Materials for photoelectric conversion elements for image sensors, image sensors, and compounds

Abstract

This invention provides a material for a photoelectric conversion element in an image sensor that exhibits excellent responsiveness, high external quantum efficiency, reduced dark current, and high thermal stability. [Solution] The image sensor includes a hole block material layer of the photoelectric conversion element material for the image sensor, represented by the following formula (1). TIFF2026106254000081.tif40170 Q is an oxygen atom, or CX 1 X 2 This represents X 1 and X 2 Z is represented by a cyano group, etc., and Z is selected from multiple sources such as nitrogen atoms and CH, with at least one of the Z atoms being a nitrogen atom.

Description

[Technical Field]

[0001] The present invention relates to materials for photoelectric conversion elements for image sensors, image sensors, and compounds. [Background technology]

[0002] Photoelectric conversion elements are widely used in solar cells, light sensors, image sensors, and the like. Their applications and market are expanding, and development is being actively pursued.

[0003] For example, Patent Document 1 discloses a photoelectric conversion element that includes a pyrimidine derivative in the hole blocking layer.

[0004] For example, Patent Document 2 discloses a photoelectric conversion element that includes a triazine derivative in the hole blocking layer. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-17302 [Patent Document 2] Korean Published Patent No. 10-2021-053141 [Overview of the project] [Problems that the invention aims to solve]

[0006] In photoelectric conversion elements used in applications such as image sensors, improvements in external quantum efficiency are desired to increase sensitivity, dark current is reduced to reduce noise, and responsiveness is improved to reduce afterimages. Furthermore, in some applications, such as automotive applications, extremely high heat resistance is required, and materials with high glass transition temperatures (T) are desirable. g They are being asked to do so.

[0007] One aspect of the present invention aims to obtain an imaging device with excellent responsiveness, high external quantum efficiency, and reduced dark current, and a material for a photoelectric conversion element for an imaging device with excellent responsiveness, high external quantum efficiency, and reduced dark current, and to realize a novel compound having extremely high heat resistance.

Means for Solving the Problems

[0008] In order to solve the above problems, an imaging device according to one aspect of the present invention is an imaging device including a layer containing a material for a photoelectric conversion element for an imaging device, wherein the material for a photoelectric conversion element for an imaging device is represented by the following formula (1);

Chemical formula

Chemical formula

[0009] Furthermore, a compound according to one aspect of the present invention is represented by the following formula (11); [ka] In the above equation (11), Q 1 is an oxygen atom, or CY 1 Y 2 It represents; Y 1 , and Y 2 Each is independently selected from a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, or a group represented by formula (12-1) or formula (12-2); [ka] In equations (12-1) and (12-2), R 12This represents identical or distinct substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heteroaromatic groups, or substituted or unsubstituted cyclic aliphatic hydrocarbon groups; * represents a coupling; Z 1 These are identical or distinct nitrogen atoms, or CR 11 Selected from, at least one nitrogen atom is selected; R 11 These are selected from the same or different groups represented by the following formula (13), hydrogen atoms, halogen atoms, and cyano groups; R 11 At least one of them is a base represented by formula (13); Two adjacent R 11 They may also form a ring by joining with each other; [ka] In the above equation (13), Ar 1 This represents identical or distinct substituted or unsubstituted di- or trivalent aromatic hydrocarbon groups, substituted or unsubstituted di- or trivalent nitrogen-containing heteroaromatic groups consisting solely of six-membered rings, substituted or unsubstituted di- or trivalent oxygen- or sulfur-containing heteroaromatic groups, or substituted or unsubstituted di- or trivalent cyclic aliphatic hydrocarbon groups; L 1 This represents identical or distinct substituted or unsubstituted di- to tetravalent aromatic hydrocarbon groups, nitrogen-containing heteroaromatic groups consisting only of substituted or unsubstituted di- to tetravalent six-membered rings, substituted or unsubstituted di- to tetravalent oxygen- or sulfur-containing heteroaromatic groups, or substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon groups; * represents a coupling; a 1 , and b 1 Each of these independently represents an integer between 1 and 3; p 1 This represents an integer between 0 and 3. [Effects of the Invention]

[0010] According to one aspect of the present invention, it is possible to obtain an image sensor with excellent responsiveness, high external quantum efficiency, and reduced dark current, and a material for a photoelectric conversion element for an image sensor with excellent responsiveness, high external quantum efficiency, and reduced dark current, and to realize a novel compound having extremely high heat resistance. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic cross-sectional view showing the stacked structure of a photoelectric conversion element for an image sensor, including a material for a photoelectric conversion element for an image sensor according to one aspect of the present invention. [Modes for carrying out the invention]

[0012] The following describes in detail the material for the photoelectric conversion element for an image sensor that is included in the layer of the photoelectric conversion element according to one aspect of the present invention.

[0013] A "photoelectric conversion element" comprising a layer containing photoelectric conversion element materials, such as materials for photoelectric conversion elements for image sensors, refers to a light-receiving element that utilizes the photoelectric effect or photovoltaic effect. Examples of light-receiving elements include photodiodes, phototransistors, image sensors (image sensors), and solar cells, with image sensors being preferred. Typically, a light-receiving element is an element that converts irradiated light into an electric current. In such cases, the light-receiving element operates on a different operating principle than a light-emitting element that converts applied electric current into light. Therefore, "materials for photoelectric conversion elements" used in "photoelectric conversion elements" refers to "materials for photoelectric conversion elements" used in "light-receiving elements," while "materials for photoelectric conversion elements" used in image sensors are referred to as "materials for photoelectric conversion elements for image sensors."

[0014] The definitions of each group in the formulas described below, and their preferred specific examples, are as follows. In this specification, functional groups such as aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are described without distinction according to their valency. For example, "phenyl group" described in the context of 1- to 3-valent aromatic hydrocarbon groups includes not only a monovalent benzene ring (i.e., a phenyl group in the narrow sense), but also a divalent benzene ring (i.e., a phenyl group) and a trivalent benzene ring (i.e., a benzenetriyl group). Similarly, "pyridyl group" includes "pyridylene group" and "pyridinetriyl group".

[0015] <Materials for photoelectric conversion elements in image sensors> An image sensor according to one aspect of the present invention is an image sensor comprising a layer containing a material for a photoelectric conversion element for an image sensor, wherein the layer contains a material for a photoelectric conversion element for an image sensor that is a compound represented by the following formula (1).

[0016] By using a material for a photoelectric conversion element for an image sensor that has Q as specifically shown in formula (1) below, and is a compound having a tetracyclic nitrogen-containing ring in which at least one of the multiple Z atoms is a nitrogen atom, an image sensor with excellent responsiveness, high external quantum efficiency, and reduced dark current can be obtained.

[0017] [ka]

[0018] The terms Q and Z shown in equation (1) above will be explained in detail below.

[0019] [Q] In equation (1), Q is an oxygen atom or CX 1 X 2 It represents. The material for the photoelectric conversion element of an image sensor, represented by formula (1), contains Q, which allows the LUMO level of the material for the photoelectric conversion element of an image sensor to be deepened, thereby increasing the response speed of the photoelectric conversion element of the image sensor. From the viewpoint of achieving such effects, Q is either an oxygen atom or CX 1 X 2 This represents X 1 and X 2 Each of these can be independently selected from a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, a group represented by formula (2-1), or a group represented by formula (2-2). Q is an oxygen atom, or CX 1 X 2 X 1 and X 2 Each of these is preferably independently a cyano group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and more preferably an oxygen atom or C(CN)2.

[0020] X 1 , and / or X 2 However, in the case of substituted or unsubstituted aryl groups, examples of such aryl groups include, but are not limited to, phenyl groups, naphthyl groups, phenanthryl groups, biphenyl groups, and phenyl groups substituted with cyano groups.

[0021] X 1 , and / or X 2 However, in the case of a substituted or unsubstituted heteroaryl group, examples of such heteroaryl groups include, but are not limited to, a pyridyl group, a quinolyl group, a pyridylphenyl group, and a pyridyl group substituted with a cyano group.

[0022] X 1 , and / or X 2 However, if it is an acyl group represented by the following formula (2-1), R 1Preferably, these are selected from identical or different substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heteroaromatic groups, or substituted or unsubstituted cyclic aliphatic hydrocarbon groups.

[0023] [ka]

[0024] More specifically, for example, the acyl group represented by formula (2-1) above includes, but is not limited to, the groups represented by G-1 to G-12 below. Here, * in each of G-1 to G-12 represents CX 1 X 2 This represents the bonding position with the carbon atom.

[0025] [ka]

[0026] X 1 , and / or X 2 However, if it is an ester group represented by the following formula (2-2), then, just like the acyl group represented by the above formula (2-1), R 1 Preferably, these are selected from identical or different substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heteroaromatic groups, or substituted or unsubstituted cyclic aliphatic hydrocarbon groups. [ka]

[0027] Examples of the group represented by formula (2-2) include, but are not limited to, the ester groups represented by G-13 to G-24 below. Here, * indicates CX in each of G-13 to G-24. 1 X 2 This represents the bonding position with the carbon atom.

[0028] [ka]

[0029] [Z] In formula (1), Z is the same or different nitrogen atom, CH and CR 2 Selected from, at least one of Z is a nitrogen atom, and at least one of the remaining Z is a CR atom. 2 Therefore, the material for the photoelectric conversion element of an image sensor can deepen the LUMO level of the material for the photoelectric conversion element of an image sensor by having at least one of the Z atoms shown in formula (1) be a nitrogen atom, thereby increasing the response speed of the photoelectric conversion element of the image sensor. From the viewpoint of achieving such effects, it is preferable that the material for the photoelectric conversion element of an image sensor represented by formula (1) has one or more nitrogen atoms, and from the viewpoint of ease of synthesis, the number of Z atoms that become nitrogen atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0030] Specifically, the material for the photoelectric conversion element for the image sensor represented by formula (1) is more preferably represented by any of the following formulas (1-1) to (1-3).

[0031] [ka]

[0032] In formulas (1-1) to (1-3), Q is the same as the definition in equation (1) above. W stands for CH or CR 2 It represents.

[0033] [R 2 ] In equation (1), Z is CR 2 When expressed as R 2 Preferably, these are the same or different groups represented by the following formula (3), a hydrogen atom, a halogen atom, or a cyano group.

[0034] [ka]

[0035] In formula (3) above, Ar is selected, either identically or differently, from substituted or unsubstituted divalent-trivalent aromatic hydrocarbon groups, substituted or unsubstituted divalent-trivalent heteroaromatic groups, and substituted or unsubstituted divalent-trivalent cyclic aliphatic hydrocarbon groups; L is selected from the same or different substituted or unsubstituted di- to tetravalent aromatic hydrocarbon groups, substituted or unsubstituted di- to tetravalent heteroaromatic groups, and substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon groups; a and b each independently represent integers between 1 and 3; p represents an integer between 0 and 3, and * represents a combination.

[0036] R 2 In terms of having excellent properties as a material for photoelectric conversion elements for image sensors, it is preferable that it be a group represented by formula (3), a hydrogen atom, or a cyano group. Furthermore, from the viewpoint of improving the thermal stability of the layer of the image sensor and the solubility of the material for photoelectric conversion elements for image sensors, thereby improving the ease of production of the material for photoelectric conversion elements for image sensors, in formula (1), R 2 If is a group represented by formula (3), the number of such groups is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and even more preferably 1 or 2. Also, R 2 If is a cyano group, the number of cyano groups is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. Also, two adjacent R 2 These elements may join together to form a ring.

[0037] [Ar] In formula (3), Ar represents, either identical or differently, a substituted or unsubstituted divalent to trivalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to trivalent heteroaromatic group, or a substituted or unsubstituted divalent to trivalent cyclic aliphatic hydrocarbon group. More specifically, the number of carbon atoms in Ar is preferably 2 to 50, more preferably 3 to 30, and even more preferably 6 to 26, either identical or differently. A larger number of carbon atoms in Ar within the above range can enhance the thermal stability of the layer in the image sensor. A smaller number of carbon atoms in Ar within the above range can enhance the solubility of the photoelectric conversion element material for the image sensor, thereby increasing the ease of manufacturing the photoelectric conversion element material for the image sensor. Thus, by appropriately selecting the number of carbon atoms in Ar, it is possible to achieve both increased ease of manufacturing of the photoelectric conversion element material for the image sensor and increased thermal stability of the layer formed from the photoelectric conversion element material in the image sensor.

[0038] The aromatic hydrocarbon group represented by Ar may be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. The aromatic hydrocarbon group is not particularly limited, but preferred examples include phenyl group, naphthyl group, phenanthryl group, anthryl group, fluorenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirofluorenyl group, pyrenyl group, fluoranthenyl group, triphenylenyl group, tetracenyl group, triptycenyl group, and chrysenyl group.

[0039] The heteroaromatic group represented by Ar is not particularly limited, but is a functional group that includes, for example, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and / or a germanium atom as heteroatoms within the aromatic ring, and may be a monoring, a linked ring containing multiple rings, or a fused ring. In the heteroaromatic group, there may be one or more heteroatoms contained within the aromatic ring. If there are two or more heteroatoms contained within the aromatic ring, these heteroatoms may be identical or different from each other.

[0040] The nitrogen-containing heteroaromatic group represented by Ar is preferably a monocyclic group such as a pyridyl group, pyrimidinyl group, pyrazyl group, triazinyl group, tetradinyl group, and imidazolyl group, and also preferably a quinolyl group, isoquinolyl group, quinoxalyl group, azaanthryl group, diazaanthryl group, triazaanthryl group, tetraazaanthryl group, azaphenanthryl group, diazaphenanthryl group, triazaphenanthryl group, tetraazaphenanthryl group, azapyrenyl group, diazapyrenyl group, triazapyrenyl group, tetraazapyrenyl group, azafluoranthenyl group, diazafluoranthenyl group The condensed ring may consist only of six-membered rings such as triazafluoranthenyl group, tetraazafluoranthenyl group, azatriphenylenyl group, diazatriphenylenyl group, triazatriphenylenyl group, tetraazatriphenylenyl group, pentaazatriphenylenyl group, and hexaazatriphenylenyl group, or it may be a condensed ring containing rings other than six-membered rings such as oxazolyl group, pyrrolyl group, imidazolyl group, triazolyl group, thiadiazolyl group, oxadiazolyl group, benzothiazolyl group, benzoxazolyl group, benzothiadiazolyl group, and benzoxadiazolyl group. Due to the availability of raw materials, nitrogen-containing heteroaromatic groups consisting only of six-membered rings are more preferred.

[0041] Preferred oxygen-containing heteroaromatic groups represented by Ar include, for example, heteroaromatic monocyclic groups such as furyl groups, benzofuryl groups, dibenzofuryl groups, benzonaphthofuryl groups, xanthenyl groups, dibenzodioxynyl groups, fluorenonyl groups, and benzoxadiazolyl groups, which are fused rings of heteroaromatic monocyclic groups.

[0042] Preferred sulfur-containing heteroaromatic groups represented by Ar include, for example, heteroaromatic monocyclic groups such as thienyl groups, benzothienyl groups, dibenzothienyl groups, thioxanthenyl groups, and fused heteroaromatic monocyclic rings such as thianthrenyl groups.

[0043] Examples of cyclic aliphatic hydrocarbon groups represented by Ar include adamantyl, diamantyl, norbornyl, cyclopentyl, and cyclohexyl groups. From the viewpoint of enhancing the thermal stability of the layer of the photoelectric conversion element, adamantyl or diamantyl groups having 10 or more carbon atoms are preferred.

[0044] In Ar, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups may or may not have substituents. In other words, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are substituted or unsubstituted. Examples of substituents that these functional groups may have include deuterium atoms, cyano groups, halogen atoms, alkyl halides, acyl groups, nitro groups, sulfonyl groups, phosphoryl groups, C1-C20 alkyl groups, alkenyl groups, and cycloalkyl groups, C1-C10 alkoxy groups, groups represented by -P(=O)(Ar')2, groups represented by -S(=O)2Ar', groups represented by -S(=O)Ar', groups represented by -B(Ar')2, groups represented by -B(OAr')2, groups represented by -Si(Ar')3, aromatic hydrocarbon groups with C6-C30, and heteroaryl groups with C3-C30 (Ar' represents an aryl group or a heteroaryl group).

[0045] Preferred groups to which Ar is substituted with -P(=O)(Ar')2 include, for example, triphenylphosphine oxide group, diphenylnaphthylphosphine oxide group, diphenylphenanthrylphosphine oxide group, diphenyl(dimethylfluorenyl)phosphine oxide group, diphenyl(diphenylfluorenyl)phosphine oxide group, and diphenylspirobiofluorenylphosphine oxide group.

[0046] Furthermore, preferred groups to which Ar is substituted with -S(=O)2Ar' include, for example, a diphenyl sulfone group and a dibenzothiophene-5,5-dioxide group, which can be forms of aromatic groups having 6 to 26 carbon atoms and having at least one sulfone group.

[0047] When the compound, which is a material for a photoelectric conversion element for an image sensor, as shown in formula (1), has multiple Ar atoms, each Ar atom may be the same or different, but it is preferable that they be the same from the viewpoint of ease of manufacture.

[0048] [L] In formula (3), L represents the same or different substituted or unsubstituted di- to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetravalent heteroaromatic group, or a substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon group.

[0049] The aromatic hydrocarbon group represented by L may be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. The aromatic hydrocarbon group is not particularly limited, but preferred examples include phenyl group, naphthyl group, phenanthryl group, anthryl group, fluorenyl group, dimethylfluorenyl group, spirofluorenyl group, pyrenyl group, fluoranthenyl group, triphenylenyl group, tetracenyl group, and chrysenyl group.

[0050] The heteroaromatic group represented by L is not particularly limited, but is a functional group that includes a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, and / or germanium atom as heteroatoms on the aromatic ring, and may be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. Examples of heteroaromatic groups include nitrogen-containing heteroaromatic groups, oxygen-containing heteroaromatic groups, and sulfur-containing heteroaromatic groups, as exemplified by Ar above. Nitrogen-containing heteroaromatic groups are preferred, and specific examples are not particularly limited, but pyridyl groups, pyrimidinyl groups, pyrazyl groups, and triazinyl groups are more preferred.

[0051] Examples of cyclic aliphatic hydrocarbon groups represented by L include, like Ar, cyclic aliphatic hydrocarbon groups having 10 or more carbon atoms, such as the adamantyl group and diamantyl group mentioned above.

[0052] In L, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups may or may not have substituents. In other words, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are either substituted or unsubstituted. Specific examples of substituents that these functional groups may have are the same as the specific examples of substituents that Ar may have.

[0053] [a,b] In equation (3), a and b each independently represent integers from 1 to 3, and are more preferably integers of 1 or 2. The material for the photoelectric conversion element for the image sensor shown in equation (1) can be optimized by optimizing a and b in equation (3) within this range, thereby reducing the glass transition temperature (T) of the material for the photoelectric conversion element for the image sensor. g This can suppress the decrease in ) and deepen the LUMO level of the photoelectric conversion element material for the image sensor, thereby increasing the response speed of the photoelectric conversion element for the image sensor.

[0054] [p] In equation (3), p represents an integer from 0 to 3, preferably an integer from 0 to 2. The material for the photoelectric conversion element for the image sensor shown in equation (1) can be improved by optimizing p in equation (3) within this range, thereby increasing the T of the material for the photoelectric conversion element for the image sensor. g This suppresses the decrease in the LUMO level, deepens the LUMO level of the photoelectric conversion element material for the image sensor, and increases the response speed in the image sensor. Note that when p is 0, L represents a single bond, and therefore in equation (1), Ar and the tetra-ring nitrogen-containing condensed ring are directly bonded by a single bond.

[0055] In the case of a compound that is a material for an image sensor photoelectric conversion element, as shown in formula (1), if L has multiple values, each of L may be the same or different.

[0056] (Electron acceptor site) The material (1) for the photoelectric conversion element for the image sensor preferably has at least one electron acceptor region, in that it lowers the energy level of the lowest unoccupied orbital (LUMO) and improves electron transport and hole blocking properties in the image sensor.

[0057] Examples of the electron acceptor sites include, but are not limited to, aromatic hydrocarbon groups containing a five-membered ring, nitrogen-containing heteroaromatic groups in which at least one lone pair of electrons of a nitrogen atom is not incorporated into the aromatic π-conjugated system, cyano groups, carbonyl groups, phosphine oxide groups, sulfoxide groups, or sulfone groups. Furthermore, these groups may have substituents.

[0058] Furthermore, the above electron acceptor sites include, for example, heteroaromatic monocyclic groups such as fluorenyl group, spirobifluorenyl group, fluoranthenyl group, pyridyl group, pyrimidinyl group, pyrazyl group, triazinyl group, tetradinyl group, imidazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, azaanthryl group, diazaanthryl group, triazaanthryl group, tetraazaanthryl group, azaphenanthryl group, diazaphenanthryl group, triazaphenanthryl group, tetraazaphenanthryl group, azapyrenyl group, diazapyrenyl group, triazapyrenyl group, tetraazapyrenyl group, azafluoranthenyl group, diazafluoranthenyl group, triazafluor Preferred but not limited to groups such as lanthenyl, tetraazafluoranthenyl, azatriphenylenyl, diazatriphenylenyl, triazatriphenylenyl, tetraazatriphenylenyl, pentaazatriphenylenyl, hexaazatriphenylenyl, oxazolyl, pyrrolyl, imidazolyl, triazolyl, thiadiazolyl, oxadiazolyl, benzothiazolyl, benzoxazolyl, benzothiadiazolyl, and benzoxadiazolyl, as well as cyano, carbonyl, amide, imide, phosphine oxide, sulfoxide, or sulfone groups. Furthermore, these groups may have further substituents, and in the case of aromatic groups, they may have further fused rings.

[0059] Furthermore, the introduction of an electron acceptor site into the group represented by formula (3) is possible by appropriately combining known reactions (e.g., Suzuki-Miyaura cross-coupling reaction) with intermediates synthesized from commercially available reagents and known reactions (e.g., Suzuki-Miyaura cross-coupling reaction, reactions described in published Japanese Patent Publication No. 2008-280330, etc.) using commercially available reagents.

[0060] <Compound (11)> In one embodiment of the present invention, the above-described material (1) for the photoelectric conversion element for the image sensor may be a compound represented by the following formula (11). The compound represented by formula (11) is also within the scope of the present invention. [ka] In the above equation (11), Q 1 is an oxygen atom, or CY 1 Y 2 It represents; Y 1 , and Y 2 Each is independently selected from a cyano group, an ester group, an acyl group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, or a group represented by formula (12-1) or formula (12-2); [ka] In equations (12-1) and (12-2), R 12 This represents identical or distinct substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heteroaromatic groups, or substituted or unsubstituted cyclic aliphatic hydrocarbon groups; * represents a coupling; Z 1 These are identical or distinct nitrogen atoms, or CR 11 Selected from, at least one nitrogen atom is selected; R 11, either identical or distinct, represents a group, hydrogen atom, halogen atom, or cyano group represented by formula (13); R 11 At least one of them is a base represented by formula (13); Two adjacent R 11 They may also form a ring by joining with each other; [ka] In the above equation (13), Ar 1 This represents identical or distinct substituted or unsubstituted di- or trivalent aromatic hydrocarbon groups, substituted or unsubstituted di- or trivalent nitrogen-containing heteroaromatic groups consisting solely of six-membered rings, substituted or unsubstituted di- or trivalent oxygen- or sulfur-containing heteroaromatic groups, or substituted or unsubstituted di- or trivalent cyclic aliphatic hydrocarbon groups; L 1 This represents identical or distinct substituted or unsubstituted di- to tetravalent aromatic hydrocarbon groups, nitrogen-containing heteroaromatic groups consisting only of substituted or unsubstituted di- to tetravalent six-membered rings, substituted or unsubstituted di- to tetravalent oxygen- or sulfur-containing heteroaromatic groups, or substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon groups; a 1 , and b 1 Each of these independently represents an integer between 1 and 3; p 1 * represents an integer between 0 and 3, and * represents a combination.

[0061] [Q 1 ] In formula (11), Q 1 is an oxygen atom, or CY 1 Y 2 Represents Y 1 , and Y 2 Each of these can be independently selected from a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, or a group represented by formula (12-1) or formula (12-2). Q 1 is an oxygen atom, or CY 1 Y 2 Y1 and Y 2 is preferably, each independently, a cyano group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, more preferably an oxygen atom or C(CN)2

[0062] In formula (11), Y 1 and Y 2 When is selected from a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, Y 1 and Y 2 are preferably selected from the aryl groups and heteroaryl groups exemplified for X 1 and X 2 in formula (1).

[0063] In formula (11), Y 1 and Y 2 When is selected from the groups represented by the above formula (12-1) or formula (12-2), Y 1 and Y 2 are preferably selected from the acyl groups represented by G-1 to G-12 or the ester groups represented by G-13 to G-24 exemplified for X 1 and X 2 in formula (1). That is, R 12 in formula (12-1) and formula (12-2) is preferably selected from the same groups as R 1 in formula (2-1) and formula (2-2).

[0064] [Z 1 Z 1 is the same or different and is selected from a nitrogen atom or C-R 11 and at least one nitrogen atom is selected.

[0065] In other words, the compound represented by formula (11) is represented by any of the following formulas (11-1) to (11-3).

Chemical formula

[0066] ​ [R 11 ] R 11 R represents a group, hydrogen atom, halogen atom, or cyano group, which is the same or different from the group represented by formula (13), and 11 At least one of them is a base represented by equation (13), and two adjacent R 1 These elements may join together to form a ring.

[0067] [Ar 1 ] Ar 1 Ar represents identical or distinct substituted or unsubstituted di- or trivalent aromatic hydrocarbon groups, nitrogen-containing heteroaromatic groups consisting only of substituted or unsubstituted di- or trivalent six-membered rings, substituted or unsubstituted di- or trivalent oxygen- or sulfur-containing heteroaromatic groups, or substituted or unsubstituted di- or trivalent cyclic aliphatic hydrocarbon groups. 1 The number of carbon atoms is the same or different, preferably 2 to 50, more preferably 3 to 30, and even more preferably 6 to 26. 1 By having a larger number of carbon atoms within the above-mentioned range, the thermal stability of the layers in the image sensor can be enhanced. 1 By having a smaller carbon number within the above range, the solubility of the material for the photoelectric conversion element of the image sensor can be increased, and the ease of manufacturing the material for the photoelectric conversion element of the image sensor can be improved. Furthermore, the layer formation in the material for the photoelectric conversion element of the image sensor, i.e., the film-forming ability in the coating process of the material for the photoelectric conversion element of the image sensor can be improved. Thus, Ar 1 By appropriately selecting the number of carbon atoms, it is possible to achieve both increased ease of manufacturing for the photoelectric conversion element material (1) for image sensors and increased thermal stability of the layer formed from the photoelectric conversion element material (1) in the image sensor.

[0068] Ar 1The aromatic hydrocarbon group represented by can be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. The aromatic hydrocarbon group is not particularly limited, but preferred examples include phenyl group, naphthyl group, phenanthryl group, anthryl group, fluorenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirofluorenyl group, pyrenyl group, fluoranthenyl group, triphenylenyl group, tetracenyl group, triptycenyl group, and chrysenyl group.

[0069] Ar 1 The nitrogen-containing, oxygen-containing, or sulfur-containing heteroaromatic group represented by is not particularly limited, but for example, it is a functional group that contains a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and / or a germanium atom as heteroatoms within the aromatic ring, and may be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. In the heteroaromatic group, there may be one or more heteroatoms contained within the aromatic ring. If there are two or more heteroatoms contained within the aromatic ring, the heteroatoms may be the same or different from each other.

[0070] Ar 1 The nitrogen-containing heteroaromatic group represented by is preferably a monocycle such as a pyridyl group, pyrimidinyl group, pyrazyl group, triazinyl group, and tetradinyl group, and may be a fused ring consisting only of six-membered rings such as a quinolyl group, isoquinolyl group, quinoxalyl group, azaanthryl group, diazaanthryl group, triazaanthryl group, tetraazaanthryl group, azaphenanthryl group, diazaphenanthryl group, triazaphenanthryl group, tetraazaphenanthryl group, azapyrenyl group, diazapyrenyl group, triazapyrenyl group, tetraazapyrenyl group, azatriphenylenyl group, diazatriphenylenyl group, triazatriphenylenyl group, tetraazatriphenylenyl group, pentaazatriphenylenyl group, and hexaazatriphenylenyl group.

[0071] Ar 1The oxygen-containing heteroaromatic group represented by is preferably a heteroaromatic monocycle such as a furyl group, a condensed ring of a heteroaromatic monocycle such as a benzofuryl group, a dibenzofuryl group, a benzonaphthofuryl group, a xanthenyl group, a dibenzodioxynyl group, a fluorenonyl group, or a benzoxadiazolyl group.

[0072] Ar 1 The sulfur-containing heteroaromatic group represented by is preferably a heteroaromatic monocycle such as a thienyl group, or a fused ring of a heteroaromatic monocycle such as a benzothienyl group, dibenzothienyl group, thioxanthenyl group, or thianthrenyl group.

[0073] Ar 1 Examples of cyclic aliphatic hydrocarbon groups represented by include adamantyl, diamantyl, norbornyl, cyclopentyl, and cyclohexyl groups. From the viewpoint of enhancing the thermal stability of the layer of the photoelectric conversion element, adamantyl or diamantyl groups having 10 or more carbon atoms are preferred.

[0074] Ar 1 In this context, aromatic hydrocarbon groups, nitrogen-containing, oxygen-containing, or sulfur-containing heteroaromatic groups, and cyclic aliphatic hydrocarbon groups may or may not have substituents. In other words, aromatic hydrocarbon groups, heteroaromatic groups, and cyclic aliphatic hydrocarbon groups are substituted or unsubstituted. Examples of substituents that these functional groups may have include deuterium atoms, cyano groups, halogen atoms, alkyl halides, acyl groups, nitro groups, sulfonyl groups, phosphoryl groups, C1-C20 alkyl groups, alkenyl groups, and cycloalkyl groups, C1-C10 alkoxy groups, groups represented by -P(=O)(Ar')2, groups represented by -S(=O)2Ar', groups represented by -S(=O)Ar', groups represented by -B(Ar')2, groups represented by -B(OAr')2, groups represented by -Si(Ar')3, aromatic hydrocarbon groups with 6-C30 carbon atoms, and heteroaryl groups with 3-C30 carbon atoms (Ar' represents an aryl group or a heteroaryl group).

[0075] Ar 1However, preferred groups to be substituted with -P(=O)(Ar')2 include, for example, triphenylphosphine oxide group, diphenylnaphthylphosphine oxide group, diphenylphenanthrylphosphine oxide group, diphenyl(dimethylfluorenyl)phosphine oxide group, diphenyl(diphenylfluorenyl)phosphine oxide group, and diphenylspirobiofluorenylphosphine oxide group.

[0076] Also, Ar 1 However, preferred groups to be substituted with -S(=O)2Ar' include, for example, a diphenyl sulfone group and a dibenzothiophene-5,5-dioxide group, which can be forms of aromatic groups having 6 to 26 carbon atoms and having at least one sulfone group.

[0077] The compound shown in formula (11) is Ar 1 If you have multiple Ar 1 Each of these may be the same or different, but from the viewpoint of ease of manufacture, they are preferably the same.

[0078] [L 1 ] In formula (11), L 1 This represents, either identical or distinct, a substituted or unsubstituted di- to tetravalent aromatic hydrocarbon group, a nitrogen-containing heteroaromatic group consisting only of a substituted or unsubstituted di- to tetravalent six-membered ring, a substituted or unsubstituted di- to tetravalent oxygen- or sulfur-containing heteroaromatic group, a substituted or unsubstituted di- to tetravalent heteroaromatic group, or a substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon group.

[0079] L 1 The aromatic hydrocarbon group represented by can be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. The aromatic hydrocarbon group is not particularly limited, but preferred examples include phenyl group, naphthyl group, phenanthryl group, anthryl group, fluorenyl group, dimethylfluorenyl group, spirofluorenyl group, pyrenyl group, fluoranthenyl group, triphenylenyl group, tetracenyl group, and chrysenyl group.

[0080] L 1 The nitrogen-containing, oxygen-containing, or sulfur-containing heteroaromatic groups represented by are not particularly limited, but are functional groups that include a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, and / or germanium atom as heteroatoms on an aromatic ring, and can be monocyclic, linked rings, or fused rings containing multiple rings. Examples of heteroaromatic groups include the above-mentioned Ar 1 Examples include nitrogen-containing heteroaromatic groups, oxygen-containing heteroaromatic groups, and sulfur-containing heteroaromatic groups consisting only of a 6-membered ring, with nitrogen-containing heteroaromatic groups being preferred. Specific examples are not limited to pyridyl groups, pyrimidinyl groups, pyrazyl groups, triazinyl groups, etc., but are more preferred.

[0081] L 1 Examples of cyclic aliphatic hydrocarbon groups represented by include Ar 1 Similarly, examples include cyclic aliphatic hydrocarbon groups having 10 or more carbon atoms, such as the adamantyl group and diamantyl group mentioned above.

[0082] L 1 In this, the aromatic hydrocarbon group, nitrogen-containing, oxygen-containing, or sulfur-containing heteroaromatic group, and cyclic aliphatic hydrocarbon group may or may not have substituents. In other words, the aromatic hydrocarbon group, nitrogen-containing, oxygen-containing, or sulfur-containing heteroaromatic group, and cyclic aliphatic hydrocarbon group are substituted or unsubstituted. Specific examples of substituents that these functional groups may have are Ar 1 These are the same as the specific examples of substituents that it can have.

[0083] [a 1 ,b 1 ] a 1 , and b 1 Each of these independently represents an integer from 1 to 3, and is more preferably an integer of 1 or 2. The material for the photoelectric conversion element for the image sensor shown in formula (11) is a 1 , and b 1By optimizing each of these within this range, the glass transition temperature (T) of the photoelectric conversion element material for the image sensor can be optimized. g This can suppress the decrease in ) and deepen the LUMO level of the photoelectric conversion element material for the image sensor, thereby increasing the response speed of the photoelectric conversion element for the image sensor.

[0084] [p 1 ] p 1 p represents an integer between 0 and 3, preferably an integer between 0 and 2. The material for the photoelectric conversion element for the image sensor shown in formula (11) is p 1 By optimizing within this range, the T of the photoelectric conversion element material for the image sensor is achieved. g This suppresses the decrease in the LUMO level, deepens the LUMO level of the photoelectric conversion element material for the image sensor, and increases the response speed in the image sensor. 1 If L is 0, 1 represents a single bond, and therefore in equation (11), Ar 1 The four nitrogen-containing condensed rings are directly bonded by single bonds.

[0085] The compound shown in formula (11), which is a material for a photoelectric conversion element for an image sensor, is L 1 If you have multiple L 1 Each of these may be the same or may be different.

[0086] (Electron acceptor site) The material (11) for the image sensor photoelectric conversion element preferably has at least one electron acceptor site in the group represented by equation (12) in order to lower the energy level of the lowest unoccupied orbital (LUMO) and increase the response speed in the image sensor photoelectric conversion element.

[0087] Preferred specific examples of compounds represented by formulas (1) and (11) are shown below, but are not limited to these.

[0088] [ka]

[0089]

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[0091]

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[0130] Furthermore, the material for a photoelectric conversion element for an image sensor (1) and the material for a photoelectric conversion element for an image sensor (11) according to one aspect of the present invention can be synthesized by appropriately combining known reactions (for example, the Suzuki-Miyaura cross-coupling reaction).

[0131] <Materials for photoelectric conversion elements in image sensors, hole block materials for image sensors> A material for a photoelectric conversion element for an image sensor according to one aspect of the present invention consists of or includes a compound represented by formula (1) (for example, a compound represented by formula (11)). The applications of the material for an image sensor according to one aspect of the present invention will be described below. As described above, the material for a photoelectric conversion element for an image sensor can be suitably used in layers of an image sensor, such as the photoelectric conversion layer and the hole blocking layer, due to its ability to achieve both response speed and external quantum efficiency.

[0132] Furthermore, the material for the photoelectric conversion element for an image sensor according to one aspect of the present invention has high T g By possessing this property, changes in the film state, such as crystallization caused by annealing during the manufacturing of the photoelectric conversion element, are prevented. As a result, a decrease in the external quantum efficiency in an image sensor formed from the image sensor photoelectric conversion element material according to one aspect of the present invention is prevented, and the dark current is reduced. Therefore, the image sensor photoelectric conversion element material according to one aspect of the present invention can be suitably used as a photoelectric conversion element material and hole block material for image sensors, where resistance to annealing after the formation of the photoelectric conversion layer is required.

[0133] A material for a photoelectric conversion element for an image sensor according to one aspect of the present invention can be used, for example, as a hole block material, which is a material for a photoelectric conversion layer in an image sensor, or a material for a hole block layer in said image sensor.

[0134] A material for a photoelectric conversion element for an image sensor according to one aspect of the present invention includes a framework represented by the above formula (1). The material for a photoelectric conversion element for an image sensor, including the framework represented by formula (1), and the hole block material contribute to the fabrication of a material for a photoelectric conversion element for an image sensor that has excellent response speed and external quantum efficiency characteristics.

[0135] <Regarding the LUMO level> For the material for a photoelectric conversion element used in an imaging device, it may be necessary to rapidly move the charges generated in the photoelectric conversion layer in order to reduce dark current, improve external quantum efficiency, and improve response speed. For the rapid movement of charges, it is preferable that the LUMO levels of the n-type semiconductor material in the photoelectric conversion layer and the material used for the hole-blocking layer are close. For example, when fullerene (C60) is used in the photoelectric conversion layer, the LUMO level of the hole-blocking layer is preferably, as quantum chemical calculation values obtained by density functional theory (DFT) as described later, successively, -2.0 eV or less, -2.1 eV or less, -2.2 eV or less, -2.3 eV or less, -2.4 eV or less, -2.5 eV or less, -2.6 eV or less, -2.7 eV or less, -2.8 eV or less, -2.9 eV or less, -3.0 eV or less. Further, the LUMO level of the hole-blocking layer is not limited, but may be -5.0 eV or more, and preferably -4.0 eV or more.

[0136] In an imaging device according to one aspect of the present invention, the LUMO level of the material for a photoelectric conversion element used in the imaging device is a value calculated by quantum chemical calculation, and the optimization of the molecular structure and the calculation of the LUMO level can be obtained by density functional theory (DFT) under the calculation conditions of the B3LYP functional and the 6-31G(d) basis function using the Gaussian program.

[0137] <Regarding the glass transition temperature> The material for a photoelectric conversion element used in the formation of a layer included in an imaging device according to one aspect of the present invention is a material for a photoelectric conversion element represented by formula (1), and the glass transition temperature of these materials for a photoelectric conversion element represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with the imaging device, that is, the photoelectric conversion element for the imaging device, the glass transition temperature is preferably 130°C or higher, more preferably 140°C or higher, and still more preferably 150°C or higher. This glass transition temperature is a value obtained from differential scanning calorimetry.

[0138] The differential scanning calorimeter and test conditions are as follows. Differential scanning calorimeter model: DSC7020 manufactured by Hitachi High-Tech; Operating conditions: The glass transition temperature was determined from the peaks when scanning twice under the conditions of a heating rate of 10 °C / min and a temperature range of 40 °C to 400 °C.

[0139] <Regarding amorphousness> As a material for a photoelectric conversion element as an image pickup device according to one aspect of the present invention, or a material for a photoelectric conversion element for an image pickup device represented by formula (1), it is preferable that the vapor deposition film of the material forms an amorphous layer. When the vapor deposition film is a crystal layer, the interface with the adjacent layer will not be uniform, which becomes a defect factor of the element.

[0140] The method for confirming whether the vapor deposition film is an amorphous layer is not particularly limited, but can be confirmed by methods commonly used by those skilled in the art, for example, by visually judging the presence or absence of crystallization, or by XRD measurement of the vapor deposition film, such as the absence of sharp diffraction peaks.

[0141] <Image pickup device> An image pickup device according to one aspect of the present invention, comprising a layer containing a material for a photoelectric conversion element for an image pickup device according to one aspect of the present invention.

[0142] The configuration of the image pickup device is not particularly limited, and examples thereof include the configurations of (i) to (vi) shown below.

[0143] (i) First electrode / Photoelectric conversion layer / Second electrode (ii) First electrode / Hole blocking layer / Photoelectric conversion layer / Second electrode (iii) First electrode / Photoelectric conversion layer / Electron blocking layer / Second electrode (iv) First electrode / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Second electrode (v) First electrode / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Hole transport layer / Second electrode (vi) First electrode / Electron transport layer / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Hole transport layer / Second electrode

[0144] Hereinafter, an image sensor according to one aspect of the present invention will be described in more detail with reference to Figure 1, using the configuration described in (v) above as an example. Figure 1 is a schematic cross-sectional view showing an example of a stacked configuration of an image sensor comprising a layer containing a material for a photoelectric conversion element for an image sensor according to one aspect of the present invention.

[0145] The image sensor 100 comprises a first electrode 1, a hole blocking layer 2, a photoelectric conversion layer 3, an electron blocking layer 4, a hole transport layer 5, and a second electrode 6 in this order. However, some of these layers may be omitted, or other layers may be added. Of the above layers, the hole blocking layer 2, the photoelectric conversion layer 3, the electron blocking layer 4, and the hole transport layer 5 constitute the organic layer 10.

[0146] The image sensor 100 shown in Figure 1 may specifically be an imaging photoelectric conversion element. Light enters the image sensor 100 from below the transparent first electrode 1 and is received by the photoelectric conversion layer 3, which is a light-receiving layer. The direction of light incidence is not particularly limited; the second electrode 6 may be transparent, and light may be incident from the second electrode 6.

[0147] The image sensor 100, due to the difference in carrier density in each layer and the internal electric field resulting from the difference in work function between the first electrode 1 and the second electrode 6, causes electrons to move to the first electrode 1 and holes to move to the second electrode 6 from the charge (holes and electrons) generated by light reception in the photoelectric conversion layer 3. Furthermore, charge can also be moved by applying a voltage between the first electrode 1 and the second electrode 6. Thus, the first electrode 1 acts as an electron collecting electrode, and the second electrode 6 acts as a hole collecting electrode.

[0148] Each layer may be replaced with another layer having a different name or function, as needed. Examples of layers with different names or functions include, for example, a hole transport layer, other names for which could be used, such as a hole injection layer, work function adjustment layer, or hole transport enhancement layer.

[0149] Note that in Figure 1, the substrate provided on the underside of the first electrode 1 is omitted. There are no particular limitations on the substrate here; for example, a glass plate, quartz plate, or plastic plate can be used. Also, in a configuration where light is incident from the substrate side, the substrate is transparent to the wavelength of light. Note that the substrate may be provided on the side of the second electrode 6. The above layers will be described below.

[0150] [Layer containing materials for photoelectric conversion elements in image sensors] An image sensor, which is one embodiment of a photoelectric conversion element, may contain the material for image sensor photoelectric conversion elements represented by formula (1) above in one or more layers selected from the group consisting of a photoelectric conversion layer and a layer between the photoelectric conversion layer and a second electrode. In the example configuration shown in Figure 1, the image sensor 100 contains the material for image sensor photoelectric conversion elements in at least one layer selected from the group consisting of a hole block layer 2 and a photoelectric conversion layer 3. In one embodiment of the present invention, it is preferable that the hole block layer 2 contains the material for image sensor photoelectric conversion elements. This has the effect of rapidly moving the necessary charge while controlling the reverse movement of holes.

[0151] Furthermore, the photoelectric conversion element material for the image sensor represented by formula (1) above may be included in multiple layers of the image sensor, and if an electron transport layer is provided, the electron transport layer may also contain the photoelectric conversion element material for the image sensor.

[0152] The following describes an imaging photoelectric conversion element 100 in which the hole block layer 2 contains a material for photoelectric conversion elements.

[0153] [First electrode 1] A first electrode 1 is provided on the substrate.

[0154] In the case of an image sensor configured such that light passes through a first electrode and is incident on a photoelectric conversion layer 3, the first electrode 1 may be formed of a transparent material that allows the light to pass through or substantially allows the light to pass through.

[0155] The transparent material used for the lower electrode, which is the first electrode 1, is not particularly limited, but examples include 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, and metal sulfides such as zinc sulfide.

[0156] Furthermore, if the image sensor 100 is configured such that light enters the photoelectric conversion layer 3 only from the second electrode 6 side, the light transmission characteristics of the first electrode 1 are not important. Therefore, examples of materials that can be used for the first electrode 1 in this case include gold, iridium, molybdenum, palladium, and platinum.

[0157] [Hole block layer 2] A hole blocking layer 2 is provided between the first electrode 1 and the photoelectric conversion layer 3, which will be described later as a light-receiving layer.

[0158] The hole blocking layer 2 has the role of transporting electrons generated in the photoelectric conversion layer 3 to the first electrode 1, and blocking the movement of holes from the photoelectric conversion layer 3 to the first electrode 1, which is the electron transport destination. Depending on the application, it may also have the role of blocking hole injection from the first electrode 1.

[0159] The hole block layer 2 may further include a conventionally known hole block material (electron transport material) in addition to the photoelectric conversion element material for the image sensor shown in formula (1) above. Conventionally known hole-blocking materials (electron transport materials) include, for example, bis(8-hydroxyquinolinate)manganese, tris(8-hydroxyquinolinate)aluminum, tris(2-methyl-8-hydroxyquinolinate)aluminum, BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen(4,7-diphenyl-1,10-phenanthroline), BAlq(bis(2-methyl-8-quinolinolate)-4-(phenylphenolate)aluminum), 4,6-bis(3,5-di(pyridine-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide.

[0160] The hole block layer 2 may be a single-layer structure made of one or more materials, or it may be a laminated structure made of multiple layers of the same or different compositions.

[0161] [Photoelectric conversion layer 3] A photoelectric conversion layer 3, which acts as a light-receiving layer, is provided between the hole-blocking layer 2 and the electron-blocking layer 4, which will be described later. The material for the photoelectric conversion layer 3 can be a material that has photoelectric conversion capabilities.

[0162] The photoelectric conversion layer 3 may be a single-layer structure made of one or more materials, or a laminated structure made of multiple layers with the same or different compositions. In particular, in order to increase the photoelectric conversion efficiency, it is preferable that the photoelectric conversion layer 3 consists of layers containing at least two materials (organic components).

[0163] Examples of materials used in the photoelectric conversion layer 3, which is a single-layer structure made of one type of material, include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, and so on.

[0164] Examples of materials used in the photoelectric conversion layer 3, which is a single-layer structure composed of two materials, include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, and (ii) fullerene and its derivatives. The photoelectric conversion layer 3 made of these materials may be formed by pre-mixing the powders and then depositing them, or by co-depositing them in any proportion.

[0165] The photoelectric conversion layer 3, which is a single-layer structure composed of three materials, can be formed using a combination of the following: (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, (ii) fullerene and its derivatives, and (iii) a hole transport material. The photoelectric conversion layer 3 composed of these materials may be formed by pre-mixing the powders and then depositing them, or by co-depositing them in any proportion.

[0166] (i) 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 and boron subnaphthalocyanine chloride (SubNC).

[0167] (ii) Specific examples of fullerenes and their derivatives include

[60] fullerene,

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

[60] PCBM).

[0168] (iii) The hole transport material may be any known hole transport material. Examples of hole transport materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthiothiophene compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, crisenodithiophene compounds, benzothiobenzothiophene compounds, indolocarbazole compounds, and the like. Among these, fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, crisenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are preferred, with fluorene compounds, crisenodithiophene compounds, benzothienobenzothiophene compounds, or indolocarbazole compounds being more preferred.

[0169] 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, and naphtho[2,3-b]naphtho[2' Examples include [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, criseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, and the following compounds (ic-1), (ic-2), and (ic-3).

[0170] [ka]

[0171] Furthermore, the material for the photoelectric conversion element of the image sensor is not limited to being contained only in the photoelectric conversion layer. For example, the material for the photoelectric conversion element of the image sensor may also be contained in a layer adjacent to the photoelectric conversion layer 3 (hole block layer 2 or electron block layer 4).

[0172] [Electronic Block Layer 4] An electron blocking layer 4 is provided between the photoelectric conversion layer 3 and the hole transport layer 5.

[0173] The electron blocking layer 4 has the role of transporting holes generated in the photoelectric conversion layer 3 from the photoelectric conversion layer 3 to the second electrode 6, and blocking the movement of electrons generated in the photoelectric conversion layer 3 towards the second electrode 6. Depending on the application, it may also have the role of blocking electron injection from the second electrode 6.

[0174] The electron blocking layer 4 may be a single-layer structure made of one or more materials, or it may be a laminated structure made of multiple layers of the same or different compositions. For example, it may be a two-layer structure including a photoelectric conversion layer 3 made of a material specialized for electron blocking and an adjacent layer, and a hole transport layer 5 made of a material specialized for hole transport and an adjacent layer.

[0175] The electron blocking layer 4 preferably contains a known hole transport material. Examples of known hole transport materials include the same materials used in the photoelectric conversion layer 3 described above.

[0176] [Hole transport layer 5] A hole transport layer 5 is provided between the electron blocking layer 4 and the second electrode 6, which will be described later. The hole transport layer 5 is provided to promote hole transport from the electron blocking layer 4 to the second electrode 6. This promotion of hole transport is brought about by the hole transport material changing the internal electric field through interaction with the surrounding material. In addition, when the second electrode 6 is formed by sputtering, the hole transport layer 5 plays a role in reducing damage to the organic layer (e.g., the electron blocking layer 4) during sputtering.

[0177] The hole transport layer 5 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), etc.

[0178] The hole transport layer 5 may be a single-layer structure made of one or more materials, or a multilayer structure of two or more layers, with the number of layers in the multilayer structure preferably being 2 to 4, more preferably 2 or 3, and even more preferably 2. The hole transport layer 5 may, for example, have the above materials and a conventionally known hole transport material. Examples include conventionally known hole transport materials, and further, the same as those used in the photoelectric conversion layer 3 described above.

[0179] [Second electrode 6] A second electrode 6 is provided on the hole transport layer 5.

[0180] Examples of materials for the second electrode 6 include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, gold, and rare earth metals.

[0181] [Method of forming each layer] Each layer, excluding the first electrode 1 and the second electrode 6 described above, can be formed by thinning the material of each layer (along with binder resin and other materials and solvents as needed) using known methods such as vacuum deposition, spin coating, casting, or the LB (Langmuir-Blodgett method).

[0182] There are no particular restrictions on the thickness of each layer formed in this way, and it can be selected as appropriate depending on the situation, but it is usually in the range of 5 nm to 5 μm.

[0183] The first electrode 1, which is the lower electrode, and the second electrode 6, which is the upper electrode, can be formed by thinning the electrode material using methods such as vapor deposition or sputtering. A pattern may be formed through a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after the thin film has been formed by vapor deposition or sputtering.

[0184] The film thickness of the first electrode 1 and the second electrode 6 is preferably 1 μm or less, and more preferably 10 nm to 200 nm.

[0185] An image sensor equipped with a photoelectric conversion element according to one aspect of the present invention can be applied, for example, to image sensors in digital cameras and digital video cameras, and to image sensors built into mobile phones and the like.

[0186] 〔summary〕 An image sensor according to embodiment 1 of the present invention is an image sensor comprising a layer containing a material for a photoelectric conversion element for an image sensor, The material for the photoelectric conversion element for the image sensor is represented by the following formula (1); [ka] In equation (1) above, Q is an oxygen atom, or CX 1 X 2 It represents; X 1 , and X 2 Each is independently selected from a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, or a group represented by formula (2-1) or formula (2-2); [ka] In equations (2-1) and (2-2), R 1 This represents identical or distinct substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heteroaromatic groups, or substituted or unsubstituted cyclic aliphatic hydrocarbon groups; * represents a coupling; Z is either identical or distinct from nitrogen atoms, CH, and CR. 2 Selected from, with at least one nitrogen atom each, and CR 2 and are selected; R 2 These are selected from the same or different groups represented by the following formula (3), halogen atoms, and cyano groups; R 2 At least one of them is a base represented by equation (3); Two adjacent R 2 They may also form a ring by joining with each other; [ka] In the above formula (3), Ar represents, either identical or distinct, a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group, a substituted or unsubstituted divalent or trivalent heteroaromatic group, or a substituted or unsubstituted divalent or trivalent cyclic or aliphatic hydrocarbon group; L represents the same or different substituted or unsubstituted di- to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetravalent heteroaromatic group, or a substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon group; * represents a coupling; a and b each independently represent integers between 1 and 3; p represents an integer between 0 and 3.

[0187] Furthermore, in the image sensor according to embodiment 2 of the present invention, it is more preferable that the group represented by formula (3) has at least one electron acceptor portion in embodiment 1.

[0188] Furthermore, in the image sensor according to embodiment 3 of the present invention, it is more preferable that the electron acceptor portion in embodiment 2 is selected from a fluorenyl group, a spirobifluorenyl group, a fluoranthenyl group, a pyridyl group, a pyrimidinyl group, a pyrazyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a cyano group, a carbonyl group, an amide group, an imide group, a phosphine oxide group, a sulfoxide group, and a sulfone group.

[0189] Furthermore, the material for a photoelectric conversion element for an image sensor according to embodiment 4 of the present invention is a material for a photoelectric conversion element for an image sensor that forms the layer provided in any of embodiments 1 to 3, and may include a compound represented by formula (1).

[0190] Furthermore, the compound according to aspect 5 of the present invention is a compound represented by the following formula (11): [ka] In the above equation (11), Q 1 is an oxygen atom, or CY 1 Y 2 It represents; Y1 , and Y 2 Each is independently selected from a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, or a group represented by formula (12-1) or formula (12-2); [ka] In equations (12-1) and (12-2), R 12 This represents identical or distinct substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heteroaromatic groups, or substituted or unsubstituted cyclic aliphatic hydrocarbon groups; * represents a coupling; Z 1 These are identical or distinct nitrogen atoms, or CR 11 Selected from, at least one nitrogen atom is selected; R 11 These are selected from the same or different groups represented by the following formula (13), hydrogen atoms, halogen atoms, and cyano groups; R 11 At least one of them is a base represented by formula (13); Two adjacent R 11 They may also form a ring by joining with each other; [ka] In the above equation (13), Ar 1 This represents identical or distinct substituted or unsubstituted di- or trivalent aromatic hydrocarbon groups, substituted or unsubstituted di- or trivalent nitrogen-containing heteroaromatic groups consisting solely of six-membered rings, substituted or unsubstituted di- or trivalent oxygen- or sulfur-containing heteroaromatic groups, or substituted or unsubstituted di- or trivalent cyclic aliphatic hydrocarbon groups; L 1This represents identical or distinct substituted or unsubstituted di- to tetravalent aromatic hydrocarbon groups, nitrogen-containing heteroaromatic groups consisting only of substituted or unsubstituted di- to tetravalent six-membered rings, substituted or unsubstituted di- to tetravalent oxygen- or sulfur-containing heteroaromatic groups, or substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon groups; * represents a coupling; a 1 , and b 1 Each of these independently represents an integer between 1 and 3; p 1 This represents an integer between 0 and 3.

[0191] The compound according to embodiment 6 of the present invention is, in embodiment 5, Q 1 However, oxygen atoms, or CY 1 Y 2 and; Y 1 , and Y 2 However, it is more preferable that each of them be independently a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a hydrogen atom.

[0192] The compound according to embodiment 7 of the present invention is, in embodiment 5 or 6, Q 1 However, it is more preferable that it be an oxygen atom or C(CN)2.

[0193] In the compound according to embodiment 8 of the present invention, it is more preferable that in any of embodiments 5 to 7, the group represented by formula (13) has at least one electron acceptor site.

[0194] The material for a photoelectric conversion element for an image sensor according to embodiment 9 of the present invention contains any of the compounds of embodiments 5 to 8.

[0195] In the embodiment 10 of the present invention, the material for the photoelectric conversion element for an image sensor is preferably a hole block material in the embodiment 9.

[0196] The image sensor according to embodiment 11 of the present invention comprises a layer containing the material for the photoelectric conversion element for the image sensor according to embodiment 9 or 10.

[0197] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. [Examples]

[0198] The present invention will be described in more detail below based on examples, but the present invention is not to be limited in any way by these examples.

[0199] [ 1 H-NMR measurement] 1 For 1H-NMR measurements, a Bruker ASCEND 400 (400MHz; manufactured by BRUKER) was used. 1 ¹H-NMR was measured using deuterated chloroform (CDCl3) as the measurement solvent and tetramethylsilane (TMS) as the internal standard.

[0200] <Synthesis Example-1> 2-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2-yl)phenyl)-7-oxo-7H-naphtho[1,2,3-de]quinoline-1-carbonitrile(A-76)

[0201] [ka]

[0202] Under an argon atmosphere, 2-(4-bromophenyl)-7-oxo-7H-naphtho[1,2,3-de]quinoline-1-carbonitrile (1.6 g, 3.9 mmol), 2-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.5 g, 3.9 mmol), and tetrakis(triphenylphosphine)palladium (0.14 g, 0.12 mmol) were suspended in THF (40 mL). 2M potassium carbonate aqueous solution (5.9 mL, 12 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered and washed with water, methanol, and hexane. The resulting solid was dissolved in hot toluene, stirred with activated carbon, and then filtered hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered to obtain 2-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)phenyl)-7-oxo-7H-naphtho[1,2,3-de]quinoline-1-carbonitrile (A-76) (0.80 g, 35%).

[0203] 1 H-NMR(400MHz,CDCl3)δ(ppm):9.55(brd,J=8.4Hz,1H),8.77(dd,J=7.4,1.3Hz,1H),8.62(dd,J=7. 8,1.5Hz,1H),8.50(dd,J=8.4,1.5Hz,1H),8.08(dd,J=8.4,7.4Hz,1H),7.98(brd,J=8.4Hz,2H),7. 91(ddd,J=8.4,7.8,1.5Hz,1H),7.81(ddd,J=7.8,7.8,1.5Hz,1H),7.73(m,3H),7.50(brd,J=7.6Hz ,1H),7.47-7.40(m,4H),7.32(dd,J=7.6,1.7Hz,1H),7.05-7.00(m,4H),5.53(s,1H),5.50(s,1H).

[0204] <Synthesis Example-2> 4'-(4-(1-cyano-7-oxo-7H-naphtho[1,2,3-de]quinoline-2-yl)phenyl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (A-142)

[0205] [ka]

[0206] Under an argon atmosphere, 2-(4-bromophenyl)-7-oxo-7H-naphtho[1,2,3-de]quinoline-1-carbonitrile (0.10 g, 0.24 mmol), 4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (0.11 g, 0.27 mmol), and dichlorobis(triphenylphosphine)palladium (5.1 mg, 7.3 μmol) were suspended in THF (2.5 mL). 2M potassium carbonate aqueous solution (0.40 mL, 0.80 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered and washed with water, methanol, and hexane. The resulting solid was dissolved in hot toluene, stirred with activated carbon, and then filtered hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered to obtain 4'-(4-(1-cyano-7-oxo-7H-naphtho[1,2,3-de]quinoline-2-yl)phenyl)-[1,1':2',1”-terphenyl]-4,4”-dicarbonitrile (A-142) (20 mg, 13%).

[0207] 1H-NMR(400MHz,CDCl3)δ(ppm):9.57(brd,J=8.1Hz,1H),8.79(dd,J=7.2,1.3Hz,1H),8.64(dd,J=7.7,1.3Hz,1H),8.53(dd,J=8.3,1.3Hz,1H),8.12(dd,J =8.2,7.2Hz,1H),8.08(brd,J=8.5Hz,2H),7.96-7.81(m,5H),7.76(d,J=1.3 Hz,1H),7.62-7.56(m,5H),7.32(brd,J=8.5Hz,2H),7.28(brd,J=8.5Hz,2H).

[0208] <Synthesis Example-3> 2-(4'-(6-(4-cyanophenyl)-4-phenylpyridine-2-yl)-[1,1'-biphenyl]-4-yl)-7-oxo-7H-naphtho[1,2,3-de]quinoline-1-carbonitrile (A-178)

[0209] [ka]

[0210] Under an argon atmosphere, 2-(4-bromophenyl)-7-oxo-7H-naphtho[1,2,3-de]quinoline-1-carbonitrile (0.10 g, 0.24 mmol), 4-(4-phenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine-2-yl)benzonitrile (0.13 g, 0.27 mmol), and dichlorobis(triphenylphosphine)palladium (5.1 mg, 7.3 μmol) were suspended in THF (2.5 mL). 2M potassium carbonate aqueous solution (0.40 mL, 0.80 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered and washed with water, methanol, and hexane. The resulting solid was dissolved in hot toluene, stirred with activated carbon, and then filtered hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered to obtain 2-(4'-(6-(4-cyanophenyl)-4-phenylpyridine-2-yl)-[1,1'-biphenyl]-4-yl)-7-oxo-7H-naphtho[1,2,3-de]quinoline-1-carbonitrile (A-178) (20 mg, 12%).

[0211] 1 H-NMR(400MHz,CDCl3)δ(ppm):9.57(brd,J=8.1Hz,1H),8.79(dd,J=7.2,1.3Hz,1H),8. 63(dd,J=7.9,1.3Hz,1H),8.54(dd,J=8.3,1.3Hz,1H),8.37(brd,J=8.5Hz,2H),8.33(b rd,J=8.5Hz,2H),8.11(dd,J=8.3,7.3Hz,1H),8.07(brd,J=8.5,2H),8.05(d,J=1.3Hz, 1H),7.96-7.90(m,4H),7.88(brd,J=8.5Hz,2H),7.85-7.77(m,5H),7.61-7.50(m,3H).

[0212] <Synthesis Example-4> 4'-(4-(7-oxo-1-phenyl-7H-naphtho[1,2,3-de]quinoline-2-yl)phenyl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (A-145)

[0213] [ka]

[0214] Under an argon atmosphere, 2-(4-bromophenyl)-1-phenyl-7H-naphtho[1,2,3-de]quinoline-7-one (1.5 g, 3.2 mmol), 4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1':2',1''-terphenyl]-4,4''-dicarbononitrile (1.5 g, 36 mmol), and tetrakis(triphenylphosphine)palladium (0.11 g, 0.097 mmol) were suspended in THF (32 mL). 2M potassium carbonate aqueous solution (5.4 mL, 11 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. After adding water to the reaction solution, the solid was filtered and washed with water, methanol, and hexane. The resulting solid was washed with hot toluene, dissolved in chloroform, stirred with activated carbon, and then filtered through Celite. By removing the solvent from the filtrate, 4'-(4-(7-oxo-1-phenyl-7H-naphtho[1,2,3-de]quinoline-2-yl)phenyl)-[1,1':2',1''-terphenyl]-4,4''-dicarbonitrile (A-145) was obtained (0.85g, 40%).

[0215] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.76(dd,J=7.3,1.4Hz,1H),8.55(dd,J=8.3,1.4Hz,1H),8.51(dd,J=8.0,1.2Hz,1H),8.00(dd,J=8.3,7.3Hz ,1H),7.73(dd,J=8.0,1.8Hz,1H),7.63(d,J=1.8Hz,1H),7.60-7.45(m,8H),7.40-7.32(m,5H),7.29-7.17(m,7H),7.14(brd,J=8.3Hz,1H).

[0216] <Glass transition temperature and LUMO level> The glass transition temperatures of compounds (A-76), (A-142), (A-178), and (A-145) from Synthesis Examples 1 to 4, as well as comparative compound 1 described in Reference 1, were measured using a differential scanning calorimeter (Hitachi High-Tech DSC7020) with an aluminum pan at a sweep rate of 10°C / min. For the LUMO level, density functional theory (DFT) was performed using Gaussian16 software with the B3LYP functional and 6-31G(d) basis function calculation conditions to optimize the molecular structure and calculate the LUMO level. The obtained glass transition temperatures and LUMO levels (calc.LUMO) are summarized in Table 1 below. Table 2 summarizes the LUMO levels of compounds (A-605), (A-606), (A-607), (A-608), (A-609), and (A-610), which were calculated by optimizing their molecular structures using Gaussian16 software, similar to compound (A-76).

[0217] [ka]

[0218] [Table 1]

[0219] [Table 2]

[0220] The results from Tables 1 and 2 above show that, as a material for photoelectric conversion elements, the compound represented by formula (1) exhibits superior thermal stability of the film compared to comparative compound 1, and furthermore / or a deeper (lower in the positive direction) calculated LUMO level (calc. LUMO) than the comparative compound.

[0221] <Example of element - 1 (see Figure 1)> As shown in Figure 1, an image sensor 100 was fabricated as a photoelectric conversion element having a stacked structure consisting of a first electrode 1, a hole blocking layer 2, a photoelectric conversion layer 3, an electron blocking layer 4, a hole transport layer 5, and a second electrode 6. The dark current, external quantum efficiency, and responsiveness of the image sensor were evaluated.

[0222] (Preparation of the first electrode 1) As a substrate with the first electrode on its surface, a glass substrate with a transparent ITO electrode was prepared, which had a 2 mm wide indium-tin (ITO) film (thickness 110 nm) patterned in stripes. Next, this substrate was cleaned with isopropyl alcohol and then surface-treated by ozone ultraviolet cleaning.

[0223] (Preparation for vacuum deposition) After cleaning and surface treatment, each layer was deposited using a vacuum deposition method onto the substrate, thereby forming a laminated structure of each layer.

[0224] First, the glass substrate is introduced into the vacuum deposition chamber, and 7.0 × 10 -5 The pressure was reduced to Pa. Then, each layer was fabricated according to the deposition conditions for each layer, in the following order.

[0225] (Preparation of hole block layer 2) A hole block layer 2 was fabricated by depositing a 10 nm thick film of the sublimation-purified compound (A-145) at a rate of 0.03 nm / second.

[0226] (Fabrication of photoelectric conversion layer (light receiving layer) 3) A photoelectric conversion layer 3 was fabricated by depositing N,N-dimethylquinacridone and C60 in a 4:1 (mass ratio) ratio to a thickness of 120 nm. The deposition rate was 0.15 nm / second.

[0227] (Fabrication of the electronic block layer 4) Compound (ic-3) was deposited at a rate of 0.10 nm / second to create a 10 nm thick electron blocking layer 4. (ic-3) was synthesized using the method described in Japanese Patent Application Publication No. 2018-193371.

[0228] (Preparation of hole transport layer 5) The 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 / second to create a 10 nm thick hole transport layer 5.

[0229] (Fabrication of the second electrode 6) Finally, a metal mask was positioned perpendicular to the ITO stripes on the substrate, and the second electrode 6, which is the upper electrode, was deposited. Specifically, silver was deposited at a rate of 0.1 nm / second to a thickness of 80 nm to fabricate the second electrode 6, which is the upper electrode.

[0230] Based on the above, as example 1 of the element, an area of ​​4 mm² is provided as shown in Figure 1. 2 A photoelectric conversion element 100 for imaging was fabricated. The film thickness of each element was measured using a stylus-type film thickness gauge (DEKTAK, Bruker).

[0231] Furthermore, this element was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less. The sealing was performed using bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation) to seal the glass sealing cap and the film-deposited substrate (element).

[0232] (Comparative Example of Element-1) In Element Example-1, an imaging photoelectric conversion element (Element Comparative Example-1) was fabricated using the same method as in Element Example-1, except that comparative compound 1 described in Reference Document 1 was used.

[0233] The dark current, external quantum efficiency, and response time were evaluated when a voltage of 2.6V was applied to the image sensor fabricated as described above. Dark current was measured using a Keithley 2636B source measure unit. External quantum efficiency was measured using a solar cell spectroscopic sensitivity analyzer (Soma Optical Co., Ltd.). The illumination wavelength was 560nm, and the intensity was 50μW / cm². 2 The measurement was performed using the following method. Response time was measured by applying a light pulse and then measuring the time it took for the current value to return to its pre-irradiation state.

[0234] Note that the dark current, external quantum efficiency, and response time are relative values ​​with the results from Comparative Example 1 set as the baseline 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. The obtained measurement results are shown in the table below.

[0235] <Evaluation results for Element Example 1 and Element Comparative Example 1> Table 3 below shows the evaluation results for external quantum efficiency, responsiveness, and dark current for each of Element Example-1 and Element Comparative Example-1.

[0236] [Table 3]

[0237] The results in the table above demonstrate that by forming a layer using compounds represented by equations (1) and (11) as materials for the photoelectric conversion element for image sensors, a photoelectric conversion element for imaging sensors can be realized that exhibits superior responsiveness, higher external quantum efficiency, and reduced dark current compared to the case where a layer is formed using comparative compound 1. [Industrial applicability]

[0238] An image sensor equipped with a photoelectric conversion element according to one aspect of the present invention can be applied, for example, to image sensors in digital cameras and digital video cameras, image sensors built into mobile phones and the like, and image input devices for driver assistance systems. [Explanation of symbols]

[0239] 1. First electrode 2 Hole block layer 3. Photoelectric conversion layer (light receiving layer) 4 Electron Block Layer 5. Hole transport layer 6. Second electrode 10 Organic layer 100 image sensors

Claims

1. An image sensor comprising a layer containing a material for a photoelectric conversion element for an image sensor, The material for the photoelectric conversion element for the image sensor is represented by the following formula (1): 【Chemistry 1】 In the above formula (1), Q is an oxygen atom, or CX １ X ２ It represents; X １ , and X ２ Each is independently selected from a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, a group represented by formula (2-1), or formula (2-2); 【Chemistry 2】 In equations (2-1) and (2-2), R １ This represents the same or different substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaromatic group, or a substituted or unsubstituted cyclic aliphatic hydrocarbon group; * represents a coupling; Z is either the same or different nitrogen atom, C-H, and C-R ２ Selected from, with at least one nitrogen atom and C-R ２ and were selected; R ２ These are selected from the same or different groups represented by the following formula (3), halogen atoms, and cyano groups; R ２ at least one of which is a group represented by formula (3); Two adjacent R ２ They may also join with each other to form a ring; 【Transformation 3】 In the above formula (3), Ar represents the same or different substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group, a substituted or unsubstituted divalent or trivalent heteroaromatic group, or a substituted or unsubstituted divalent or trivalent cyclic or aliphatic hydrocarbon group; L represents the same or different substituted or unsubstituted di- to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted di- to tetravalent heteroaromatic group, or a substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon group; * represents a coupling; a and b each independently represent integers between 1 and 3; p represents an integer between 0 and 3, and is an image sensor element.

2. The image sensor according to claim 1, wherein the group represented by formula (3) has at least one electron acceptor portion.

3. The image sensor according to claim 2, wherein the electron acceptor group is selected from a fluorenyl group, a spirobifluorenyl group, a fluoranthenyl group, a pyridyl group, a pyrimidinyl group, a pyrazyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a cyano group, a carbonyl group, an amide group, an imide group, a phosphine oxide group, a sulfoxide group, and a sulfone group.

4. A material for a photoelectric conversion element for an image sensor, comprising a compound represented by formula (1), for forming the layer of the image sensor described in claim 1.

5. Compound represented by the following formula (11): 【Chemistry 4】 In the above formula (11), Q １ is an oxygen atom, or CY １ Y ２ It represents; Y １ , and Y ２ Each is independently selected from a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, a group represented by formula (12-1), or formula (12-2); 【Transformation 5】 In equations (12-1) and (12-2), R １２ This represents the same or different substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaromatic group, or a substituted or unsubstituted cyclic aliphatic hydrocarbon group; * represents a coupling; Z １ These are identical or distinct nitrogen atoms, or C-R １１ Selected from, at least one nitrogen atom is selected; R １１ These are selected from the same or different groups represented by the following formula (13), hydrogen atoms, halogen atoms, and cyano groups; R １１ At least one of them is a base represented by formula (13); Two adjacent R １１ They may also join with each other to form a ring; 【Transformation 6】 In the above formula (13), Ar １ This represents, either identical or distinct, a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group, a nitrogen-containing heteroaromatic group consisting only of a substituted or unsubstituted divalent or trivalent six-membered ring, a substituted or unsubstituted divalent or trivalent oxygen-containing or sulfur-containing heteroaromatic group, or a substituted or unsubstituted divalent or trivalent cyclic aliphatic hydrocarbon group; L １ This represents, either identical or distinct, a substituted or unsubstituted di- to tetravalent aromatic hydrocarbon group, a nitrogen-containing heteroaromatic group consisting only of a substituted or unsubstituted di- to tetravalent six-membered ring, a substituted or unsubstituted di- to tetravalent oxygen- or sulfur-containing heteroaromatic group, or a substituted or unsubstituted di- to tetravalent cyclic aliphatic hydrocarbon group; * represents a coupling; a １ , and b １ Each of these independently represents an integer between 1 and 3; p １ This represents an integer between 0 and 3.

6. Q １ However, oxygen atoms, or CY １ Y ２ And; Y １ , and Y ２ The compound according to claim 5, wherein each is independently a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a hydrogen atom.

7. Q １ However, oxygen atoms, or C (CN) ２ The compound according to claim 5.

8. The compound according to claim 7, wherein the group represented by formula (13) has at least one electron acceptor site.

9. A material for a photoelectric conversion element for an image sensor, comprising the compound described in any one of claims 5 to 8.

10. A hole-blocking material, which is a material for a photoelectric conversion element for an image sensor according to claim 9.

11. An image sensor comprising a layer containing the material for a photoelectric conversion element for an image sensor as described in claim 9.

Images