Photoelectric conversion device for image sensor

Abstract

To provide a photoelectric conversion device for an image sensor that has low dark current and excellent responsiveness.SOLUTION: A photoelectric conversion device for an image sensor contains a compound represented by the formula (1) in the figure. (In the formula (1), Ar represents a substituted or unsubstituted aromatic hydrocarbon group or heteroaromatic group having two or more fused or condensed rings, and L represents a substituted or unsubstituted aromatic hydrocarbon group or heteroaromatic group having three or more condensed rings.)SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photoelectric conversion element for an image sensor. [Background technology]

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

[0003] In recent years, market demand for photoelectric conversion elements for image sensors has been increasing, and materials that are excellent in terms of dark current, external quantum efficiency, and response speed are being sought. Under these circumstances, the possibility of various polycyclic compounds as the mother nucleus of new materials has been continuously explored and studied. As polycyclic compounds, Patent Document 1 discloses derivatives with benzothienobenzothiophene as the mother nucleus. Furthermore, Patent Document 2 discloses various mother nuclei in addition to benzothienobenzothiophene. Patent Document 3 discloses unsubstituted dibenzo[g,p]chrysene. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2015 / 163349 [Patent Document 2] International Publication No. 2020 / 022421 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-258438 Summary of the Invention [Problem to be solved by the invention]

[0005] One object of one embodiment of the present invention is to propose a photoelectric conversion element for an imaging device using a compound having a new mother nucleus, while the possibility of using various polycyclic compounds as the mother nucleus of a new material is being explored and investigated.

[0006] Another object of one embodiment of the present invention is to provide a photoelectric conversion element for an imaging device that has low dark current and excellent response. Incidentally, Patent Document 3 describes the use of unsubstituted dibenzo[g,p]chrysene as a crystalline layer between a photoelectric conversion layer and an upper electrode. However, Patent Document 3 makes no mention of the molecular structural characteristics of dibenzo[g,p]chrysene or an amorphous film containing dibenzo[g,p]chrysene. In addition, the dibenzo[g,p]chrysene described in Patent Document 3 does not provide any knowledge on improving the performance of a photoelectric conversion element for an imaging device. [Means for solving the problem]

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

[0008] An aspect of the present disclosure relates to the following photoelectric conversion element for an imaging device.

[0009] [1] A photoelectric conversion element for an imaging device, comprising a compound represented by the following formula (1): [ka] (In formula (1), Ar is an optionally substituted aromatic hydrocarbon group having two or more linked or fused rings, or represents an optionally substituted heteroaromatic group having two or more linked or fused rings, L is an aromatic hydrocarbon group having three or more fused rings which may be substituted, or represents an optionally substituted heteroaromatic group having three or more fused rings. [2] The photoelectric conversion element for an imaging device according to [1], wherein Ar is a linked or fused ring of two rings. [3] The photoelectric conversion element for an imaging device according to [1] or [2], wherein Ar is a group represented by any one of the following formulae (Ar1) to (Ar4): [ka] (In formulas (Ar1)~(Ar4), R a ~R j each independently represents a hydrogen atom or a substituent, R a ~R f Any one of the groups is bonded to L. [4] The R not bonded to the L a ~R j is a hydrogen atom. [5] The photoelectric conversion element for an imaging device according to any one of [1] to [4], wherein L is 3 or more and less than 10 fused rings. [6] The photoelectric conversion element for an imaging device according to any one of [1] to [4], wherein L is 3 to 6 fused rings. [7] The photoelectric conversion element for an imaging device according to any one of [1] to [6], wherein L is a group represented by the following formula (LA): [ka] (In formula (LA), X is an oxygen atom, a sulfur atom, -C(R I )(R J )- or -N(R K )-, R A ~R K Any two of the following are bonded to Ar and the nitrogen atom in the formula (1), respectively; R A ~R D are each independently a hydrogen atom, a substituent, or Y 1 ~Y 2 , or Y in the following formula (3) 3 ~Y 4 Represents, However, R A ~R D Either of the following is Y 1 ~Y 4 If Y 1 Any group adjacent to is Y 2 and Y 3 Any group adjacent to is Y 4 is. R E ~RK each independently represents a hydrogen atom or a substituent. [ka] In equations (2) and (3), Y 1 ~Y 3 represents a carbon atom, Y 4 is an oxygen atom, a sulfur atom, -C(R R )(R S )- or -N(R T )-, * represents R in the formula (LA). A ~R D represents a carbon atom in a six-membered aromatic ring to which R L ~R T each independently represents a hydrogen atom or a substituent. [8] The photoelectric conversion element for an imaging device according to any one of [1] to [7], wherein L is a group represented by any one of the following formulas (L1) to (L15): [ka] (In formulas (L1) to (L15), R 1 ~R 16 each independently represents a hydrogen atom or a substituent, R 1 ~R 16 Any two of these are bonded to Ar and the nitrogen atom in the formula (1), respectively. [9] The R that is not bonded to Ar or a nitrogen atom in the formula (1) 1 ~R 16 is a hydrogen atom.

[10] The photoelectric conversion element for an imaging device according to any one of [1] to [9], wherein the compound represented by formula (1) is any one of formulas (A-1) to (P-10) described below. [Effects of the Invention]

[0010] According to one embodiment of the present invention, a photoelectric conversion element for an imaging element with low dark current and excellent response can be provided. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view showing an example of a layer structure of a photoelectric conversion element for an imaging element including a material for a photoelectric conversion element for an imaging element according to one aspect of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, a photoelectric conversion element for an imaging device according to one aspect of the present disclosure will be described in detail.

[0013] <Photoelectric conversion element for imaging element> The photoelectric conversion element for an imaging device contains a compound represented by the following formula (1): The compound represented by the following formula (1) can be suitably used as a material for a photoelectric conversion element for an imaging device. That is, a material for a photoelectric conversion element for an imaging element according to one embodiment of the present disclosure contains a compound represented by the following formula (1). [ka] (In formula (1), Ar is an optionally substituted aromatic hydrocarbon group having two or more linked or fused rings, or represents an optionally substituted heteroaromatic group having two or more linked or fused rings, L is an aromatic hydrocarbon group having three or more fused rings which may be substituted, or represents an optionally substituted heteroaromatic group having three or more fused rings.

[0014] When the compound represented by the formula (1) has the specific structure, a photoelectric conversion element for an imaging device containing the compound represented by the formula (1) has a low dark current and excellent response.

[0015] Preferred embodiments of the definition in the above formula (1) are as follows:

[0016] <ar> (aromatic hydrocarbon group) Examples of the optionally substituted aromatic hydrocarbon group having two or more linked rings represented by Ar include a biphenyl group and a terphenyl group. Examples of the optionally substituted aromatic hydrocarbon group having two or more fused rings represented by Ar include a naphthyl group, an indenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a benzochrysenyl group, a dibenzochrysenyl group, a fluorenyl group, a benzofluorenyl group, a spirobifluorenyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, and a phenanthrylphenyl group.

[0017] When the aromatic hydrocarbon group having two or more linked or fused rings has a substituent, the substituents are preferably each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group which may have a substituent, a silyl group which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Of these, alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups are more preferred.

[0018] The phosphine oxide group as the substituent includes an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent, and is preferably a phosphine oxide group having a substituent.

[0019] The phosphine oxide group having a substituent, which is the above-mentioned substituent, is preferably a phosphine oxide group having a monocyclic, linked, or fused ring aromatic hydrocarbon group or a fused ring heteroaromatic group having 6 to 18 carbon atoms. Specific examples include groups substituted with two aryl groups, such as diphenylphosphine oxide.

[0020] The silyl group as the substituent includes an unsubstituted silyl group and a silyl group having a substituent, and a silyl group having a substituent is preferred.

[0021] The silyl group having a substituent, which is the above-mentioned substituent, is preferably a silyl group having a monocyclic, linked, or fused ring aromatic hydrocarbon group or a fused ring heteroaromatic group having 6 to 18 carbon atoms. Specific examples include groups substituted with three aryl groups, such as a triphenylsilyl group.

[0022] Examples of the boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms as the substituent include a dihydroxyboryl group (-B(OH)2), a 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl group, and a 5,5-dimethyl-[1,3,2]-dioxaborinane group.

[0023] The alkyl group as the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

[0024] The alkoxy group as the substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, and an octadecyloxy group.

[0025] Examples of the aromatic hydrocarbon group as the substituent include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, a fluoranthenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a triphenylenyl group, a spirobifluorenyl group, a diphenylfluorenyl group, a dibenzo[g]chrysenyl group, and a dibenzo[g,p]chrysenyl group.

[0026] Examples of the heteroaromatic group as the substituent include a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, a phenylpyridyl group, a pyridylphenyl group, a pyrimidyl group, a pyrazyl group, a 1,3,5-triazyl group, a 1,3,5-triazylphenyl group, a 1,3,5-triazylbiphenylyl group, a 4,6-diphenyl-1,3,5-triazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidyl group, a benzophenone ... Examples thereof include an adazolyl group, an indazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a 2,1,3-benzothiadiazolyl group, a benzoxazolyl group, a benzisoxazolyl group, a 2,1,3-benzoxadiazolyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-(4-biphenylyl)carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

[0027] (heteroaromatic group) The optionally substituted heteroaromatic group having two or more linked or fused rings represented by Ar includes a heteroaromatic group having two or more linked or fused rings containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom on the aromatic ring.

[0028] Examples of the heteroaromatic group include a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, a carbazolylphenyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, an indazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a 2,1,3-benzothiadiazolyl group, a benzoxazolyl group, a benzisoxazolyl group, a 2,1,3-benzoxadiazolyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-(4-biphenylyl)carbazolyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

[0029] In addition, when the heteroaromatic group of two or more rings linked or fused has a substituent, the substituent is preferably each independently a cyano group, a fluorine atom, a trifluoromethyl group, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group.Among these, an alkyl group, an aromatic hydrocarbon group, or a heteroaromatic group is more preferred.

[0030] The alkyl group as the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. When the aromatic hydrocarbon group has a substituent, examples of the alkyl group include the same alkyl groups as those exemplified as the substituent.

[0031] The alkoxy group as the substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. When the aromatic hydrocarbon group has a substituent, examples of the alkoxy group include the same alkoxy groups as those exemplified as the substituent.

[0032] Examples of the aromatic hydrocarbon group as the substituent include the same aromatic hydrocarbon groups as those exemplified as the substituent when the aromatic hydrocarbon group described above has a substituent.

[0033] Examples of the heteroaromatic group as the substituent include the same heteroaromatic groups as exemplified as the substituent when the aromatic hydrocarbon group described above has a substituent.

[0034] The above Ar is preferably a linked or fused ring of two rings, from the viewpoint of providing a photoelectric conversion element for an imaging device with low dark current and excellent response.

[0035] The above Ar is preferably a group represented by any one of the following formulae (Ar1) to (Ar4), from the viewpoint of providing a photoelectric conversion element for an imaging device with low dark current and excellent response. [ka] (In formulas (Ar1)~(Ar4), R a ~R j each independently represents a hydrogen atom or a substituent, R a ~R f Any one of the above is bonded to L.)

[0036] In formula (Ar1), R a ~R h The substituents represented by the formula (Ar2) and (Ar3) are the same as those exemplified when the aromatic hydrocarbon group having two or more rings linked or fused rings has a substituent. a ~R f The substituent represented by the formula (Ar4) may be the same as the substituent exemplified when the heteroaromatic group having two or more rings linked or fused together has a substituent. a ~R j Examples of the substituent represented by the formula (I) include the same substituents as those exemplified when the aromatic hydrocarbon group having two or more rings linked or fused rings has a substituent.

[0037] The above R that is not bonded to the above L a ~R j is preferably a hydrogen atom from the viewpoint of providing a photoelectric conversion element for an imaging device with low dark current and excellent response.

[0038] <l> (aromatic hydrocarbon group) Examples of the optionally substituted aromatic hydrocarbon group having three or more fused rings represented by L include a phenanthryl group, an anthryl group, a fluorenyl group, a spirobifluorenyl group, a triphenylenyl group, a pyrenyl group, a dibenzochrysenyl group, a chrysenyl group, and a benzochrysenyl group.

[0039] When the aromatic hydrocarbon group having three or more fused rings has a substituent, the substituents are preferably each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group which may have a substituent, a silyl group which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Of these, alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups are more preferred.

[0040] The alkyl group as the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group include the same alkyl groups as those exemplified as the substituents on the optionally substituted aromatic hydrocarbon group having two or more linked or fused rings represented by Ar.

[0041] The alkoxy group as the substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. Examples of the alkoxy group include the same alkoxy groups as exemplified as the substituent on the optionally substituted aromatic hydrocarbon group having two or more linked or fused rings represented by Ar.

[0042] Examples of the aromatic hydrocarbon group as the substituent include the same aromatic hydrocarbon groups as exemplified as the substituents on the optionally substituted aromatic hydrocarbon group having two or more linked or fused rings represented by Ar.

[0043] Examples of the heteroaromatic group as the substituent include the same heteroaromatic groups as exemplified as the substituent in the optionally substituted aromatic hydrocarbon group of two or more linked or fused rings represented by Ar.

[0044] (heteroaromatic group) The optionally substituted heteroaromatic group having three or more fused rings represented by L includes a heteroaromatic group having three or more fused rings and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom on the aromatic ring.

[0045] Examples of the heteroaromatic group include a benzothienobenzothiophenyl group, a benzo[2,1-b:3,4-b']bis[1]benzothiophenyl group, a benzo[1,2-b:5,4-b']bis[1]benzothiophenyl group, a benzo[1,2-b:4,5-b']bis[1]benzothiophenyl group, an 11,12-dihydro-11,12-diphenylindolo[2,3-a]carbazolyl group, a 5,7-dihydro-5,7-diphenylindolo[2,3-b]carbazolyl group, and a 5,11-dihydro-5,11-diphenylindolo[3,2-b]carbazolyl group.

[0046] In addition, when the heteroaromatic group having three or more fused rings has a substituent, the substituent is preferably each independently a cyano group, a fluorine atom, a trifluoromethyl group, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Among these, an alkyl group, an aromatic hydrocarbon group, or a heteroaromatic group is more preferred.

[0047] The alkyl group as the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group include the same alkyl groups as those exemplified as the substituents on the optionally substituted aromatic hydrocarbon group having two or more linked or fused rings represented by Ar.

[0048] The alkoxy group as the substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. Examples of the alkoxy group include the same alkoxy groups as exemplified as the substituent on the optionally substituted aromatic hydrocarbon group having two or more linked or fused rings represented by Ar.

[0049] Examples of the aromatic hydrocarbon group as the substituent include the same aromatic hydrocarbon groups as exemplified as the substituents on the optionally substituted aromatic hydrocarbon group having two or more linked or fused rings represented by Ar.

[0050] Examples of the heteroaromatic group as the substituent include the same heteroaromatic groups as exemplified as the substituent on the optionally substituted aromatic hydrocarbon group having two or more linked or fused rings represented by Ar.

[0051] From the viewpoint of providing a photoelectric conversion element for an imaging device with low dark current and excellent response, L preferably has 3 or more and less than 10 fused rings, and more preferably has 3 or more and 6 or less fused rings.

[0052] The above L is preferably a group represented by the following formula (LA), from the viewpoint of providing a photoelectric conversion element for an imaging device with low dark current and excellent response. [ka] (In formula (LA), X is an oxygen atom, a sulfur atom, -C(R I )(R J )- or -N(R K )-, R A ~R K Any two of the following are bonded to Ar and the nitrogen atom in the formula (1), respectively; R A ~R D are each independently a hydrogen atom, a substituent, or Y 1 ~Y 2 , or Y in the following formula (3) 3 ~Y 4 Represents, However, R A ~R D Either of the following is Y 1 ~Y 4 If Y 1 Any group adjacent to is Y 2 and Y 3 Any group adjacent to is Y 4 is. R E ~R K each independently represents a hydrogen atom or a substituent. [ka] In equations (2) and (3), Y 1 ~Y 3 represents a carbon atom, Y 4 is an oxygen atom, a sulfur atom, -C(R R )(R S )- or -N(R T )-, * represents R in the formula (LA). A ~R D represents a carbon atom in a six-membered aromatic ring to which R L ~R T each independently represents a hydrogen atom or a substituent.

[0053] In formula (LA), R A ~R K The substituents represented by R include the same as those exemplified when the aromatic hydrocarbon group having two or more rings linked or fused, represented by Ar in the above formula (1), has a substituent. L ~R T Examples of the substituent represented by the formula (1) include the same substituents as those exemplified when the heteroaromatic group having two or more linked or fused rings represented by Ar in the formula (1) has a substituent.

[0054] The above L is preferably a group represented by any one of the following formulae (L1) to (L15), from the viewpoint of providing a photoelectric conversion element for an imaging device with low dark current and excellent response.

[0055] [ka]

[0056] [ka]

[0057] In formulas (L1) to (L15), R 1 ~R 16 each independently represents a hydrogen atom or a substituent, R 1 ~R 16 Any two of these are bonded to Ar and the nitrogen atom in the above formula (1), respectively.

[0058] In formulas (L1) to (L15), R 1 ~R 16 In the formulae (L1) to (L15), the substituent represented by R is the same as the substituent exemplified when the aromatic hydrocarbon group having three or more fused rings has a substituent. 1 ~R 16 Examples of the substituent represented by the formula (I) include the same substituents as those exemplified when the heteroaromatic group having three or more fused rings has a substituent.

[0059] The R that is not bonded to Ar or a nitrogen atom in the formula (1) 1 ~R 16 is preferably a hydrogen atom from the viewpoint of providing a photoelectric conversion element for an imaging device with low dark current and excellent response.

[0060] The compound represented by the above formula (1) is preferably any one of the following formulae (A-1) to (P-10).

[0061] [ka]

[0062]

change

[0063]

change

[0064]

change

[0065]

change

[0066]

change

[0067]

change

[0068]

change

[0069]

change

[0070]

change

[0071]

change

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] The compound represented by the formula (1) can be synthesized by a known method. For example, it can be synthesized by a known method disclosed in CN110128330, CN110627659, US20160260901, JP2019-12747A, JP2011-84717A, JP2018-193371A, JP2019-34939A, JP2011-6397A, Japanese Patent No. 4968333A, CN109851623A, WO2012114928A, KR2011016047A.

[0080] <Uses of the compound represented by formula (1)> As described above, the compound represented by formula (1) is suitably used as a material for a photoelectric conversion element for an imaging element. The material for the photoelectric conversion element of an imaging device is preferably, for example, a charge transport material for the photoelectric conversion element of an imaging device or a charge blocking material for the photoelectric conversion element of an imaging device.The charge transport material for the photoelectric conversion element of an imaging device is preferably, for example, a hole transport material for the photoelectric conversion element of an imaging device.The charge blocking material for the photoelectric conversion element of an imaging device is preferably, for example, an electron blocking material for the photoelectric conversion element of an imaging device.

[0081] Hereinafter, a photoelectric conversion element for an image sensor according to this embodiment will be described as an example.

[0082] <Photoelectric conversion element for imaging element> The photoelectric conversion element for an image sensor of this embodiment contains the above-described material for a photoelectric conversion element for an image sensor. The configuration of the photoelectric conversion element for the imaging device is not particularly limited, but examples thereof include the following configurations (i) to (v).

[0083] (i) First electrode / photoelectric conversion layer / second electrode (ii) First electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / second electrode (iii) First electrode / photoelectric conversion layer / hole transport layer (electron blocking layer) / second electrode (iv) First electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / second electrode (v) First electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / buffer layer / second electrode

[0084] The buffer layer may be replaced with a layer having a different name or function, as needed, such as a hole injection layer or a work function adjustment layer. The photoelectric conversion element for an imaging device may contain the material for a photoelectric conversion element for an imaging device in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer), and a buffer layer. Furthermore, the photoelectric conversion element for an imaging device preferably contains the material for a photoelectric conversion element for an imaging device in the photoelectric conversion layer and / or the hole transport layer (electron blocking layer), and more preferably contains the material for a photoelectric conversion element for an imaging device in the hole transport layer (electron blocking layer). The material for a photoelectric conversion element for an imaging device may be contained in multiple layers of the photoelectric conversion element for an imaging device.

[0085] Hereinafter, the photoelectric conversion element for an image sensor will be described in more detail using the above configuration (v) as an example, with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the layered configuration of a photoelectric conversion element for an image sensor containing a material for a photoelectric conversion element for an image sensor.

[0086] The photoelectric conversion element 100 for an imaging device in Fig. 1 includes, in this order, a substrate 1, a first electrode 2, an electron transport layer (hole blocking layer) 3, a photoelectric conversion layer 4, a hole transport layer (electron blocking layer) 5, a buffer layer 6, and a second electrode 7. Note that the photoelectric conversion element for an imaging device may omit some of these layers, may have other layers added, may have a configuration in which Fig. 1 is inverted, or may have some of these layers omitted, or may have other layers added.

[0087] In the photoelectric conversion element 100 for an imaging device, light is incident from the transparent first electrode 2 or second electrode 7. Furthermore, a voltage is applied to the photoelectric conversion element 100 for an imaging device so that, of the charges (holes and electrons) generated in the photoelectric conversion layer 4, the electrons move to the first electrode 2 and the holes move to the second electrode 7. That is, in the photoelectric conversion element 100 for an imaging device, the first electrode 2 serves as an electron collecting electrode and the second electrode 7 serves as a hole collecting electrode.

[0088] [Layer containing material for photoelectric conversion element for image sensor] The photoelectric conversion element 100 for an imaging device contains a material for a photoelectric conversion element for an imaging device in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer) 3, a photoelectric conversion layer 4, a hole transport layer (electron blocking layer) 5, and a buffer layer 6. The photoelectric conversion element 100 for an imaging device preferably contains the material for a photoelectric conversion element for an imaging device in the photoelectric conversion layer 4 and / or the hole transport layer (electron blocking layer) 5, and more preferably contains the material for a photoelectric conversion element for an imaging device in the hole transport layer (electron blocking layer) 5. The material for a photoelectric conversion element for an imaging device may be contained in multiple layers of the photoelectric conversion element 100 for an imaging device.

[0089] Hereinafter, a photoelectric conversion element 100 for an imaging element in which the hole transport layer (electron blocking layer) 5 contains a material for a photoelectric conversion element for an imaging element will be described.

[0090] [Board 1] The substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate, etc. In a configuration in which light is incident from the substrate 1 side, it is preferable that the substrate 1 has high transmittance to the wavelength of light (for example, a transmittance of 80% or more, preferably a transmittance of 90% or more).

[0091] [First electrode 2] A first electrode 2 is provided on a substrate 1 . In the case of a photoelectric conversion element for an imaging device configured so that light passes through the first electrode 2 and enters the photoelectric conversion layer, it is preferable that the first electrode 2 has high transparency (for example, a transmittance of 80% or more, preferably a transmittance of 90% or more) to the wavelength of the incident light.

[0092] There are no particular limitations on the transparent material used for the first electrode 2. From the viewpoint of excellent light transmittance, the material constituting the first electrode 2 may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide.

[0093] In the case of a photoelectric conversion element for an imaging device configured so that light enters the photoelectric conversion layer only from the second electrode 7 side, the transmission characteristics of the first electrode 2 are not important. Therefore, examples of materials that can be used for the first electrode 2 in this case include sodium, sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, silver, gold, a magnesium / silver mixture, aluminum, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, indium, a lithium / aluminum mixture, iridium, molybdenum, palladium, platinum, and rare earth metals.

[0094] [Electron transport layer (hole blocking layer) 3] Between the first electrode 2 and the photoelectric conversion layer 4, an electron transport layer (hole blocking layer) 3 is provided.

[0095] The electron transport layer (hole blocking layer) 3 has the role of transporting electrons generated in the photoelectric conversion layer 4 to the first electrode 2 and the role of blocking holes generated in the photoelectric conversion layer 4 from moving to the first electrode 2.

[0096] The electron transport layer (hole blocking layer) 3 may have a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. The electron transport layer (hole blocking layer) 3 may have, for example, a two-layer structure including a layer made of a material specialized for hole blocking properties and adjacent to the photoelectric conversion layer 4, and a layer made of a material specialized for electron transport properties and adjacent to the first electrode 2.

[0097] The electron transport layer (hole blocking layer) 3 may be a layer containing a conventionally known electron transport material, such as bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide.

[0098] [Photoelectric conversion layer 4] A photoelectric conversion layer 4 is provided between the electron transport layer (hole blocking layer) 3 and a hole transport layer (electron blocking layer) 5 described later. The photoelectric conversion layer 4 contains a material having a photoelectric conversion function.

[0099] The photoelectric conversion layer 4 may be made of either an organic or inorganic material as long as it can generate signal charges according to the amount of light received. When the photoelectric conversion layer 4 is made of an organic material, the photoelectric conversion layer 4 may have a single layer structure made of one or more materials, or a laminate 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. N-type semiconductors are organic semiconductors with acceptor properties, and compounds that easily accept electrons and have high electron transport properties are used. P-type semiconductors are organic semiconductors with donor properties, and compounds that easily donate electrons and have high hole transport properties are used. When multiple materials are used in the photoelectric conversion layer 4, the combinations include, for example, an n-type semiconductor and a p-type semiconductor, an n-type semiconductor and a compound having lower acceptor properties than the n-type semiconductor, a p-type semiconductor and a compound having lower donor properties than the p-type semiconductor, etc. One type of each material may be used, or two or more types of materials may be used. The photoelectric conversion layer 4 may contain a dye compound that is excellent at absorbing specific light. The dye compound may be a compound that has lower acceptor properties than the n-type semiconductor, or a compound that has lower donor properties than the p-type semiconductor. In terms of increasing photoelectric conversion efficiency, it is desirable that the photoelectric conversion layer 4 further contains a dye compound in addition to the n-type semiconductor and the p-type semiconductor. Examples of compounds contained in the photoelectric conversion layer 4 include coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, fullerene and its derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, oxazole, oxadiazole, and triazole, naphthalenetetracarboxylic acid diimide, and hole transport materials. Among these, phthalocyanine and its derivatives, and fullerene and its derivatives are preferred. The photoelectric conversion layer 4 made of these materials may be formed, for example, by vapor deposition using a mixed powder obtained by mixing powders of the respective materials, or by co-evaporation of the respective materials in any ratio.

[0100] Specific examples of coumarin derivatives include coumarin 6 and coumarin 30. Specific examples of quinacridone derivatives include N,N-dimethylquinacridone. Specific examples of phthalocyanine derivatives include boron subphthalocyanine chloride, boron subnaphthalocyanine chloride (SubNC), F6-SubPC-OC6F5, and Cl6-SubPC-OC6. Specific examples of fullerenes and derivatives thereof include

[60] fullerene,

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

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

[0101] Specific examples of hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compounds, benzo[1,2-b:3,4-b':5,6-b'']trithiophene compounds, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2',3' :4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b']dithiophene, benzo[1,2-b:4,5-b']bis[1]benzothiophene, naphtho[1,2-b:5,6-b']bis[1]benzothiophene, chryseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, compounds represented by the following formula (ic-1), compounds represented by the following formula (ic-2), and the like.

[0102] [ka]

[0103] The material having the photoelectric conversion function described above may be contained only in the photoelectric conversion layer 4, or may also be contained in layers other than the photoelectric conversion layer 4. For example, layers adjacent to the photoelectric conversion layer 4 (electron transport layer (hole blocking layer) 3, hole transport layer (electron blocking layer) 5) may contain a material having the photoelectric conversion function.

[0104] [Hole transport layer (electron blocking layer) 5] A hole transport layer (electron blocking layer) 5 is provided between the photoelectric conversion layer 4 and a buffer layer 6 described later.

[0105] The hole transport layer (electron blocking layer) 5 has a role of transporting holes generated in the photoelectric conversion layer 4 toward the second electrode 7, and a role of blocking electrons generated in the photoelectric conversion layer 4 from moving toward the second electrode 7. The hole transport layer (electron blocking layer) 5 preferably contains the above-mentioned material for a photoelectric conversion element for an imaging element.

[0106] The hole transport layer (electron blocking layer) 5 may have a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. The hole transport layer (electron blocking layer) 5 may have, for example, a two-layer structure including a layer made of a material specialized for electron blocking properties and adjacent to the photoelectric conversion layer 4, and a layer made of a material specialized for hole transport properties and adjacent to the buffer layer 6.

[0107] The hole transport layer (electron blocking layer) 5 may further contain a conventionally known hole transport material in addition to the above-mentioned materials for a photoelectric conversion element for an imaging device. Preferred compounds and specific examples of the conventionally known hole transport material include the same as the hole transport materials described in the section on the photoelectric conversion layer 4.

[0108] [Buffer layer 6] A buffer layer 6 is provided between the hole transport layer (electron blocking layer) 5 and the second electrode 7 described below. When the second electrode 7 is formed by sputtering, the buffer layer 6 serves to reduce damage to the organic layer (for example, the hole transport layer (electron blocking layer) 5) during sputtering. In addition, by adjusting the work function of the buffer layer 6, the buffer layer 6 also serves to efficiently accept holes from the hole transport layer (electron blocking layer) 5 and accept electrons from the second electrode 7, and is therefore also called a hole injection layer or a work function adjustment layer.

[0109] The material forming the buffer layer 6 may be a known material, such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), or the like.

[0110] [Second electrode 7] A second electrode 7 is provided on the buffer layer 6 . The material of the second electrode 7 is not particularly limited, and may be, for example, sodium, sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, silver, gold, a magnesium / silver mixture, aluminum, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, indium, a lithium / aluminum mixture, iridium, molybdenum, palladium, platinum, a rare earth metal, or the like. In the case of a photoelectric conversion element for an imaging device configured so that light enters the photoelectric conversion layer from the second electrode 7 side, the material forming the second electrode 7 may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide.

[0111] [How each layer is formed] Each layer other than the first electrode 2 and the second electrode 7 can be formed by forming the material of each layer (and, if necessary, materials such as binder resin, solvent, etc.) into a thin film by a known method such as vacuum deposition, spin coating, casting, or LB (Langmuir-Blodgett) method. The thickness of each layer other than the lower electrode 2 and the upper electrode 7 is not particularly limited and can be selected appropriately depending on the situation. The thickness of each layer other than the lower electrode 2 and the upper electrode 7 is usually in the range of 5 nm to 5 μm.

[0112] The first electrode 2 and the second electrode 7 can be formed by thinning an electrode material by a method such as vapor deposition or sputtering. When the first electrode 2 and the second electrode 7 have a pattern, the pattern can be formed, for example, through a mask of a desired shape. Alternatively, after forming a thin film by vapor deposition, sputtering, or the like, a pattern of a desired shape can be formed by photolithography.

[0113] The film thickness of the first electrode 2 and the second electrode 7 may be 1 μm or less, and is preferably 10 nm or more and 200 nm or less.

[0114] An imaging element including the photoelectric conversion element according to this embodiment can be applied to, for example, imaging elements in digital cameras, digital video cameras, and imaging elements built into mobile phones and the like. Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. [Example]

[0115] The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited to these examples.

[0116] [Synthesis Reference Examples 1 to 6: Compounds (F-1), (H-1), (H-3), (H-4), (H-11), (H-14)] Compounds (F-1), (H-1), (H-3), (H-4), (H-11) and (H-14) were each synthesized by the known method disclosed in JP 2018-193371 A. The compound was identified by 1H-NMR. 1 H-NMR measurements were carried out using a Gemini200 (Varian). 1 The results of H-NMR measurement are shown below.

[0117] Compound (F-1) H-NMR (DMSO-d 6 )δ(ppm)=8.51(s,1H),8.36(d,J=8.0Hz,1H),8.08-8.14(m,3H),7.92(d,J=7.2Hz,2H),7.80 (d,8.8Hz,2H),7.55-7.63(m,11H),7.40-7.50(m,7H),7.27-7.37(m,4H),7.17-7.21(m,5H)

[0118] Compound (H-3) 1H-NMR (DMSO-d 6 )δ(ppm)=8.87-8.75(m,6H),8.28(d,J=8.0Hz,1H),8.12(d,J=2.4Hz,1H),8.08-7.99(m,3H),7.80 -7.76(m,3H),7.73-7.53(m,13H),7.49-7.40(m,6H),7.35(t,J=7.2Hz,2H),7.29(d,J=8.8Hz,4H)

[0119] Compound (H-4) 1H-NMR (DMSO-d 6 )δ(ppm)=8.98-8.90(m,3H),8.88-8.85(d,J=7.6Hz,1H),8.83-8.78(m,2H),8.38(s,1H),8.31(d,J=8.8Hz,1H),8.22(dd,J=8.8Hz,1.6Hz,1H) ,8.13(d,J=2.4Hz,1H),8.10-7.96(m,4H),7.81-7.71(m,10H),7.65(t ,J=8.4Hz,1H),7.57-7.52(m,3H),7.51-7.42(m,5H),7.38-7.32(m,6H)

[0120] Compound (H-11) 1H-NMR (DMSO-d 6 )δ(ppm)=9.11(d,J=1.6Hz,1H),9.06(d,J=9.2Hz,1H),8.94-8.84(m,1H),8.81(d,J=8.0Hz,1H),8.74-8.71(m,2H),8.28 (d,J=8.4Hz,1H),8.13-8.06(m,4H),7.88(d,J=8.4Hz,2H),7.81-7.70(m,12H),7.64(t,J=7.6Hz,1H),7.55-7.30(m,15H)

[0121] Compound (H-14) H-NMR (DMSO-d 6 )δ(ppm)=9.19(d,J=1.6Hz,1H),9.07(d,J=9.2Hz,1H),8.86-8.83(m,1H),8. 80(d,J=8.0Hz,1H),8.74-7.70(m,2H),8.58(s,1H),8.27(d,J=8.4Hz,1H),8. 20-8.07(m,5H),8.00(d,J=7.2Hz,1H),7.79-7.69(m,10H),7.64-7.45(m,8H ),7.41(t,J=7.6Hz,1H),7.36(td,J=7.6Hz,1.2Hz,2H),7.30(d,J=8.4Hz,4H)

[0122] [Element Example 1: Preparation of a photoelectric conversion element for an imaging element using compound (H-1)] As shown in Figure 1, a photoelectric conversion element 100 for an imaging device was fabricated having a layered structure consisting of a substrate 1, a first electrode 2, an electron transport layer (hole blocking layer) 3, a photoelectric conversion layer 4, a hole transport layer (electron blocking layer) 5, a buffer layer 6, and a second electrode 7, and its characteristics were evaluated.

[0123] (Preparation of Substrate 1 and First Electrode 2) A glass substrate with an indium-tin oxide (ITO) transparent electrode, patterned with a 2 mm wide stripe of ITO film (110 nm thick), was prepared as a substrate with a first electrode on its surface. The substrate was then cleaned with isopropyl alcohol and then subjected to surface treatment using ozone and ultraviolet light.

[0124] (Vacuum deposition) Each layer was laminated on the surface-treated substrate by vacuum deposition. Specifically, a glass substrate with an ITO transparent electrode was placed in a vacuum deposition chamber. -5 The pressure was reduced to 100 Pa. Then, each layer was formed in the following order according to the film formation conditions.

[0125] (Fabrication of Electron Transport Layer (Hole Blocking Layer) 3) Sublimation-purified 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine was deposited at a rate of 0.10 nm / sec to form a 10 nm thick film, thereby forming an electron transport layer (hole blocking layer) 3 .

[0126] (Fabrication of Photoelectric Conversion Layer 4) 2Ph-BTBT, F6-SubPc-OC6F5, and fullerene (C60) were co-deposited at a deposition rate ratio of 4:4:2 to form a 200 nm thick photoelectric conversion layer 4. The film formation rate was 0.15 nm / sec.

[0127] (Preparation of Hole Transport Layer (Electron Blocking Layer) 5) The sublimation-purified compound (H-1) was formed into a film having a thickness of 10 nm at a rate of 0.10 nm / second to form a hole transport layer 5.

[0128] (Fabrication of Buffer Layer 6) Sublimation-purified 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 form a 10 nm thick film, thereby forming a buffer layer 6 .

[0129] (Fabrication of Second Electrode 7) A metal mask was placed so as to be perpendicular to the ITO stripes on the substrate, and a second electrode 7 was formed. The second electrode was formed by depositing gold to a thickness of 80 nm at a gold deposition rate of 0.1 nm / sec.

[0130] Using the above method, an area of 4 mm 2 The thickness of each layer was measured using a stylus film thickness meter (DEKTAK, manufactured by Bruker).

[0131] The fabricated device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less using a glass sealing cap and bisphenol F epoxy resin (manufactured by Nagase ChemteX Corporation).

[0132] [Element Examples 2 to 6, Element Comparative Examples 1 and 2] Photoelectric conversion elements for imaging devices of element examples 2 to 6 and element comparative examples 1 and 2 were prepared in the same manner as element example 1, except that in preparing the hole transport layer (electron blocking layer) 5 of element example 1, compound (H-3), compound (H-4), compound (H-11), compound (H-14), compound (F-1), N-[1,1'-biphenyl]-4-yl-N-[4-(11,12-dihydro-11,12-diphenylindolo[2,3-a]carbazol-5-yl)phenyl][1,1'-biphenyl]-4-amine (ic-2) and 2-diphenylaminodibenzo[g,p]chrysene (X-1) were used instead of compound (H-1).

[0133] [ka]

[0134] [Measurement of dark current, external quantum efficiency and response time] The photoelectric conversion element for an image sensor fabricated as described above was applied with a voltage of 2.6 V (absolute value) so that electrons were transported to the first electrode 2 side and holes to the second electrode 7 side. The current in the dark (dark current), external quantum efficiency, and response time were evaluated. The dark current was evaluated using a Keithley Source Measure Unit 2636B. The external quantum efficiency was measured using a solar cell spectral response measurement device (Soma Optical Co., Ltd.) with irradiated light of a wavelength of 560 nm and an intensity of 50 μW / cm. 2 The response time was measured by irradiating a light pulse and measuring the time it took for the current value to return to the value before irradiation.

[0135] The results are shown in Table 1. The results shown in Table 1 are relative values, with the result of comparative element example 2 set as the reference value (1.0). A lower dark current value indicates better performance, a higher external quantum efficiency value indicates better performance, and a shorter response time indicates better performance.

[0136] [Table 1]

[0137] As shown in Table 1, the elements of the examples using the specific materials for photoelectric conversion elements for image sensors had suppressed dark current and were superior in response compared to the elements of the comparative examples. [Explanation of symbols]

[0138] 1 board 2. First electrode 3 Electron transport layer (hole blocking layer) 4 Photoelectric conversion layer 5. Hole transport layer (electron blocking layer) 6 Buffer layer 7 Second electrode 100 Photoelectric conversion element for imaging device< / l> < / ar>

Claims

1. A photoelectric conversion element for an imaging device, comprising a compound represented by the following formula (1): 【Chemical formula 1】 (In formula (1), Ar is an optionally substituted aromatic hydrocarbon group having two or more linked or fused rings, or represents an optionally substituted heteroaromatic group having two or more linked or fused rings, L is an optionally substituted aromatic hydrocarbon group having three or more condensed rings, or represents an optionally substituted heteroaromatic group having three or more fused rings.

2. The photoelectric conversion element for an imaging device according to claim 1 , wherein Ar is a linked or fused ring of two rings.

3. 3. The photoelectric conversion element for an imaging device according to claim 1, wherein Ar is a group represented by any one of the following formulas (Ar1) to (Ar4): 【Chemistry 2】 (In formulas (Ar1) to (Ar4), R a ~R ｊ each independently represents a hydrogen atom or a substituent, R a ~R ｆ Any one of the groups is bonded to the L.

4. The R that is not bonded to the L a ~R ｊ The photoelectric conversion element for an imaging device according to claim 3 , wherein is a hydrogen atom.

5. 3. The photoelectric conversion element for an imaging device according to claim 1, wherein L is 3 or more and less than 10 fused rings.

6. 3. The photoelectric conversion element for an imaging device according to claim 1, wherein L is a group consisting of 3 to 6 fused rings.

7. 3. The photoelectric conversion element for an imaging device according to claim 1, wherein L is a group represented by the following formula (LA): 【Chemistry 3】 (In formula (LA), X is an oxygen atom, a sulfur atom, or -C(R Ｉ ) (R Ｊ )- or -N(R Ｋ )-, R Ａ ~R Ｋ Any two of the following are bonded to Ar and the nitrogen atom in the formula (1), respectively; R Ａ ~R Ｄ are each independently a hydrogen atom, a substituent, or Y １ ~Y ２ or Y in the following formula (3): ３ ~Y ４ Represents, However, R Ａ ~R Ｄ Either of the following is Y １ ~Y ４ If Y １ Any group adjacent to Y ２ and Y ３ Any group adjacent to Y ４ is. R Ｅ ~R Ｋ each independently represents a hydrogen atom or a substituent. 【Chemistry 4】 In formulas (2) and (3), Y １ ~Y 3 represents a carbon atom, Y ４ is an oxygen atom, a sulfur atom, -C(R Ｒ ) (R Ｓ )- or -N(R Ｔ )-, * represents R in the formula (LA). Ａ ~R Ｄ represents a carbon atom in a six-membered aromatic ring to which is bonded, R Ｌ ~R Ｔ each independently represents a hydrogen atom or a substituent.

8. 3. The photoelectric conversion element for an imaging device according to claim 1, wherein L is a group represented by any one of the following formulas (L1) to (L15): 【Chemistry 5】 (In formulas (L1) to (L15), R １ ~R １６ each independently represents a hydrogen atom or a substituent, R １ ~R １６ Any two of these are bonded to Ar and the nitrogen atom in the formula (1), respectively.

9. Ar and the R in formula (1) that are not bonded to a nitrogen atom １ ~R １６ The photoelectric conversion element for an imaging device according to claim 8 , wherein is a hydrogen atom.

10. 3. The photoelectric conversion element for an imaging device according to claim 1, wherein the compound represented by formula (1) is any one of the following formulae (A-1) to (P-10): 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 【Chemistry 18】 【Chemistry 19】 【Chemistry 20】 【Chemical 21】 【Chemical 22】 【Chemical 23】

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