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

Abstract

The objective is to provide 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 (100) comprises a layer containing a material for a photoelectric conversion element for the image sensor, and the material for a photoelectric conversion element for the image sensor (1) has a tetrahedral three-dimensional portion (2), the three-dimensional portion (2) has a central atom (3), and portions selected from the lone pair of electrons (4) of the central atom (3) and adjacent atoms (5) of the central atom (3), and has a first annular structure containing the central atom (3) and adjacent atoms (5), and a second annular structure condensed with the first annular structure.

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. 10-2021-0053141 [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 realize a novel compound that can obtain an image sensor with excellent responsiveness, high external quantum efficiency, and reduced dark current, and a photoelectric conversion element material for an image sensor with excellent responsiveness, high external quantum efficiency, and reduced dark current, and that also has extremely high heat resistance. [Means for solving the problem]

[0008] To solve the above problems, according to one aspect of the present invention, an image sensor comprising a layer containing a material for a photoelectric conversion element for an image sensor, wherein the material for a photoelectric conversion element for an image sensor (1) has at least one tetrahedral three-dimensional portion (2), the tetrahedral three-dimensional portion (2) has a central atom (3) at the center of the tetrahedron, and at the vertices of the tetrahedron there are portions selected from a lone pair of electrons (4) of the central atom (3) and 3 or 4 adjacent atoms (5) bonded to the central atom (3), and further comprises a first annular structure and the first ring An image sensor is provided, having a second cyclic structure condensed with a first cyclic structure, wherein the first cyclic structure includes the central atom (3) and at least two of the adjacent atoms (5), and the first or second cyclic structure has at least one substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heteroaromatic group, wherein the aromatic hydrocarbon group or heteroaromatic group is a monoring, a linking ring containing multiple rings, or a fused ring, and the molecular weight of the material (1) for the image sensor photoelectric conversion element is 500 or more.

[0009] Furthermore, according to another aspect of the present invention, an image sensor is provided that includes a layer comprising a material for a photoelectric conversion element for an image sensor having at least one of the three-dimensional structures represented by the following formulas (2-1) to (2-9), including the three-dimensional portion (2), the first annular structure, and the second annular structure.

[0010] [ka]

[0011] In the above equations (2-1) to (2-9), W1 and W 2 Each of these independently represents either C-Ra or N; W 3 Each of these independently represents either C(-Ra)2 or N-Ra; Ra represents, either identical or distinct, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted hydrocarbon group, a hydrogen atom, a halogen atom, or a cyano group; The wavy line indicates the bonding site with an adjacent group; The stereostructures of formulas (2-1) to (2-9) may be unsubstituted or have substituents; The three-dimensional structures of equations (2-1) to (2-9) may be further connected to or fused with three-dimensional parts (2). At least one of the Ra is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heteroaromatic group, and the aromatic hydrocarbon group or heteroaromatic group is a monoring, a linking ring containing multiple rings, or a fused ring.

[0012] Furthermore, according to another aspect of the present invention, a compound represented by the following formula (6) having a tetrahedral stereometric part (2) is provided:

[0013] [ka]

[0014] In the above formula (6), Ar 1 ~Ar 3 Each of these independently represents 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 1 ~L 3 Each of these independently represents a 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; The number of carbon atoms in the aromatic hydrocarbon group is 6 to 28; The number of carbon atoms in the heteroaromatic group is 3 to 24; The number of carbon atoms in the cycloaliphatic hydrocarbon group is 10 to 16; a 1 、a 2 、b 1 、b 2 、c 1 、and c 2 each independently represents an integer of 1 to 3; p, q, and r each independently represent an integer of 0 to 3; Ar 1 、Ar 2 、and Ar 3 at least one of them has a three-dimensional structure containing a tetrahedral three-dimensional moiety (2) represented by formula (2-8-1);

[0015]

Chemical formula

[0016] In the formula (2-8-1), * represents the bonding site with an adjacent group; Ar 1 、Ar 2 、Ar 3 、L 1 、L 2 、and L 3 the sum of the number of cyano groups, the number of adamantyl groups, and the number of groups represented by formula (2-8-1) contained in these groups is 2 or more; The molecular weight of the compound represented by formula (6) is 550 or more.

Advantages of the Invention

[0017] According to one aspect of the present invention, an image pickup device excellent in responsiveness, having a high external quantum efficiency, and having a reduced dark current, and, for example, a photoelectric conversion element material for an image pickup device excellent in responsiveness, having a high external quantum efficiency, and having a reduced dark current can be obtained, and a novel compound having very high heat resistance can be realized.

Brief Description of the Drawings

[0018] [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]

[0019] 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.

[0020] 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."

[0021] 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".

[0022] Furthermore, the triazine rings specifically shown in each formula are distinguished from the selectively described "triazine" and "triazinyl group" by being written as "triazine ring".

[0023] <Materials for photoelectric conversion elements for image sensors (1)> The glass transition temperature of the material (1) for the photoelectric conversion element of the image sensor is preferably 140°C or higher, more preferably 145°C or higher, more preferably 150°C or higher, more preferably 155°C or higher, and even more preferably 160°C or higher. A high glass transition temperature of the material (1) for the photoelectric conversion element of the image sensor enhances the thermal stability of the layers of the image sensor.

[0024] (Stereotype (2) and central atom (3)) In the material (1) for the photoelectric conversion element for the image sensor, the central atom (3) of the three-dimensional portion (2) is preferably a carbon atom, nitrogen atom, silicon atom, phosphorus atom, or sulfur atom, more preferably a carbon atom, nitrogen atom, phosphorus atom, or sulfur atom, more preferably a carbon atom, phosphorus atom, or sulfur atom, and even more preferably a carbon atom or sulfur atom, in terms of ease of material synthesis. However, the central atom (3) is not limited to a carbon atom, nitrogen atom, silicon atom, phosphorus atom, or sulfur atom, and may be, for example, a germanium atom, tin atom, arsenic atom, antimony atom, bismuth atom, selenium atom, tellurium atom, etc.

[0025] In the material (1) for the photoelectric conversion element of an image sensor, the three-dimensional region (2) is formed such that a central atom (3) is positioned at the center, and four regions selected from one lone pair of electrons (4) of the central atom (3) and three or four adjacent atoms (5) bonded to the central atom (3) are located at the vertices of a tetrahedron. In this three-dimensional region (2), the tetrahedron is not limited to a regular tetrahedron, but also includes a distorted tetrahedron. For example, the sp3 hybrid orbital of a carbon atom is approximately a regular tetrahedron. That is, if the central atom (3) is a carbon atom, and the carbon atom takes on an sp3 hybrid orbital, and these hybrid orbitals each form covalent bonds with four adjacent atoms (5), then the three-dimensional region formed by the carbon atom (3) and the adjacent atoms is approximately a regular tetrahedron. On the other hand, for example, the sp3 hybrid orbital of a nitrogen atom as the central atom (2) is a distorted tetrahedron containing the lone pair of electrons (4) of the nitrogen atom. In other words, if the central atom (3) is a nitrogen atom, and the nitrogen atom takes on an sp3 hybrid orbital, and this hybrid orbital forms a covalent bond with each of the three adjacent atoms, then the stereolith (2) formed by the three adjacent atoms covalently bonded to the central atom (3), the nitrogen atom, and the lone pair of electrons (4) of the nitrogen atom becomes a distorted tetrahedron. When the central atom (3) is a carbon atom, a nitrogen atom, or a silicon atom, it is preferably CR4, NR3, or SiR4, but is not limited to these. However, two of the multiple Rs may bond with each other to form a single ring (first cyclic structure) containing the central atom (3), and the Rs that do not form a ring are hydrogen atoms, substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heteroaromatic groups, where the aromatic hydrocarbon group or heteroaromatic group may be a monoring, a linking ring containing multiple rings, or a fused ring, and the monorings constituting the linking ring or fused ring may be the same or different, but do not have to be the same at the same time.

[0026] On the other hand, in the three-dimensional portion (2) of the material (1) for the photoelectric conversion element for the image sensor, if the central atom (3) is, for example, a phosphorus atom or a sulfur atom, then, similar to a nitrogen atom, the hybrid orbital may be a tetrahedron type in which it contains one lone pair of electrons and forms covalent bonds with three adjacent atoms, or it may be a tetrahedron type in which it donates valence electrons to an adjacent atom (for example, an oxygen atom) and forms bonds with four adjacent atoms. For example, if the central atom (3) is a sulfur atom, and the hybrid orbital is a tetrahedron type in which it contains one lone pair of electrons and forms bonds with the sulfur atom of the central atom (3) and three adjacent atoms, then the three-dimensional portion of the three-dimensional structure (3) is a sulfoxide. However, if it is a tetrahedron type in which it forms bonds with four adjacent atoms, then the three-dimensional structure (3) is a sulfone.

[0027] When the central atom (3) is a phosphorus atom or a sulfur atom, it is preferable that it forms a tetrahedron shape by bonding with four adjacent atoms (5), respectively, in order to increase the glass transition temperature. More specifically, it is preferable that the stereomove (2) is R3P=O (phosphine oxide) or R2S(=O)2 (sulfone), but it is not limited to these. However, R is a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaromatic group, or a substituted or unsubstituted cyclic aliphatic hydrocarbon group. These groups preferably form a ring (i.e., a first cyclic structure) together in order to increase the glass transition temperature of the material (1) for the image sensor photoelectric conversion element. When R that does not form a ring is an aromatic hydrocarbon group or a heteroaromatic group, the aromatic hydrocarbon group or heteroaromatic group may be a monoring, a linking ring containing multiple rings, or a fused ring. The monorings constituting the linking ring or fused ring may be the same or different, but multiple Rs that do not form a ring will not simultaneously form the same monoring.

[0028] The neighboring atoms (5) bonded to the central atom (3) of the stereotype (2) may be selected from carbon atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, and hydrogen atoms. If the neighboring atoms (5) are selected from carbon atoms, nitrogen atoms, sulfur atoms, silicon atoms, and phosphorus atoms, then two of these neighboring atoms (5) and the central atom (3) are included in one first cyclic structure.

[0029] In the material (1) for the photoelectric conversion element for the image sensor, the first cyclic structure including the central atom (3) of the three-dimensional portion (2) is preferably a 3-membered ring, 4-membered ring, 5-membered ring, 6-membered ring, 7-membered ring, or 8-membered ring, and is more preferably a 5-membered ring or a 6-membered ring because it is easy to synthesize and the film has high thermal stability.

[0030] From the standpoint of ease of synthesis and high thermal stability of the film, the second cyclic structure in the material for the photoelectric conversion element for the image sensor (1), which contains at least one atom from the first cyclic structure, is preferably a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.

[0031] From the viewpoint of further increasing the glass transition temperature, the material (1) for the image sensor photoelectric conversion element preferably has at least one first cyclic structure having a central atom (3) and two adjacent atoms (5), and the first cyclic structure and the second cyclic structure have a fused ring structure. Here, the second cyclic structure may be a cyclic structure having a central atom (3) or a cyclic structure without a central atom (3), as long as it is fused with the first cyclic structure. Furthermore, the first cyclic structure in the material (1) for the image sensor photoelectric conversion element may have a plurality of stereometric parts (2) and their central atoms (3), in which case the material (1) for the image sensor photoelectric conversion element may have a plurality of first cyclic structures.

[0032] The glass transition temperature of the material (1) for the image sensor photoelectric conversion element is 140°C or higher; In the aforementioned photoelectric conversion element material (1) for the image sensor, the central atom (3) is a carbon atom, a nitrogen atom, a silicon atom, a phosphorus atom, or a sulfur atom; In the material (1) for the photoelectric conversion element for the image sensor, the first cyclic structure including the central atom (3) of the stereometric portion (2) is more preferably a 5-membered ring or a 6-membered ring, from the standpoint of ease of synthesis; In the material (1) for the photoelectric conversion element for the image sensor, it is preferable that the second cyclic structure, which contains at least one atom from the first cyclic structure, is a five-membered ring or a six-membered ring.

[0033] Furthermore, due to their ease of synthesis and high thermal stability of the film, the three-dimensional portion (2) in the material (1) for the photoelectric conversion element for the image sensor is a tetrahedral structure such as CR4, NR3, SiR4, R3P=O (phosphine oxide), or R2S(=O)2 (sulfone); In the material (1) for the photoelectric conversion element for the image sensor, the first cyclic structure in the three-dimensional portion (2) including the central atom (2) of the three-dimensional portion is a five-membered ring or a six-membered ring; In the material (1) for the image sensor photoelectric conversion element, it is preferable that the second cyclic structure, which contains at least one atom from the first cyclic structure, is a six-membered ring. However, R is distinct from each other and may be an aromatic hydrocarbon group, a heteroaromatic group, a cyclic aliphatic hydrocarbon group, or a hydrogen atom, and these groups may form rings with each other.

[0034] By having a tetrahedral structure, a first annular structure, and a second annular structure as described above, the chemical bond binding and intermolecular interactions in the material (1) for the photoelectric conversion element of an image sensor are strengthened, providing a novel compound and material for the photoelectric conversion element of an image sensor with a very high glass transition temperature and heat resistance. The novel compound and material for the photoelectric conversion element of an image sensor with a very high glass transition temperature and heat resistance can increase the process temperature in the image sensor fabrication process and the operating temperature range of the image sensor.

[0035] The material (1) for the photoelectric conversion element for the image sensor has at least one substituted or unsubstituted aromatic hydrocarbon group or substituted or unsubstituted heteroaromatic group linked to a first cyclic structure or a second cyclic structure, wherein the aromatic hydrocarbon group or heteroaromatic group may be a monoring, a linked ring containing multiple rings, or a fused ring, and may have an electron acceptor site as a substituent, and an aromatic hydrocarbon group or heteroaromatic group similar to Ra in formulas (2-1) to (2-9) described later may be selected.

[0036] (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.

[0037] 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 (4) 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.

[0038] Furthermore, the above electron acceptor sites include, for example, heteroaromatic monocyclic groups such as fluorenyl group, spirobifluorenyl group, fluoranthenyl group, pyridyl group, pyrimidyl 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 Examples of heteroaromatic monocyclic fused rings include, but are not limited to, groups such as thenyl group, tetraazafluoranthenyl group, azatriphenylenyl group, diazatriphenylenyl group, triazatriphenylenyl group, tetraazatriphenylenyl group, pentaazatriphenylenyl group, hexaazatriphenylenyl group, oxazolyl group, pyrrolyl group, imidazolyl group, triazolyl group, thiadiazolyl group, oxadiazolyl group, benzothiazolyl group, benzoxazolyl group, benzothiadiazolyl group, and benzoxadiazolyl group, as well as cyano group, carbonyl group, amide group, imide group, phosphine oxide group, sulfoxide group, and sulfone group. Furthermore, these groups may have substituents, and in the case of aromatic groups, they may have further fused rings.

[0039] When the stereochemical portion (2) of the material (1) for the photoelectric conversion element for the image sensor is R2S(=O)2 (sulfone), it is preferable that the material (1) for the photoelectric conversion element for the image sensor has a triazinyl group as the electron acceptor portion, and the other portions are composed of aromatic hydrocarbon groups and heteroaromatic groups. With such a configuration, the magnitude of the interaction with the light-receiving layer can be appropriately adjusted, and the dark current can be reduced.

[0040] [ka]

[0041] The material (1) for the photoelectric conversion element for the image sensor preferably has at least one of the three-dimensional structures represented by the following formulas (2-1) to (2-9), which include the three-dimensional portion (2), the first annular structure, and the second annular structure.

[0042] [ka] In the above equations (2-1) to (2-9), W 1 and W 2 Each of these independently represents C-Ra or N; W 3 Each of these independently represents either C(-Ra)2 or N-Ra; Ra represents, either identical or distinct, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted hydrocarbon group, a hydrogen atom, a halogen atom, or a cyano group; * indicates a bonding site with an adjacent group; The structures of formulas (2-1) to (2-9) may be unsubstituted, substituted, or have the above-mentioned electron acceptor moieties as substituents; The three-dimensional structures of equations (2-1) to (2-9) may be further connected to or fused with three-dimensional parts (2), for example, they may be connected or fused structures as shown in the following equation.

[0043] [ka]

[0044] In equations (2-1) to (2-7), the three-dimensional part (2) is W 1 It is expressed as follows. In equations (2-8) and (2-9), W 2 Since it is not located at the center of the tetrahedral structure, it does not correspond to the central atom (3), W 3 This can be the stereomolecule (2). In formula (2-8), sulfur (S) corresponds to the central atom (3), and in formula (2-9), phosphorus (P) corresponds to the central atom (3).

[0045] In formulas (2-1) to (2-7), the aromatic hydrocarbon group represented by Ra may be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. The aromatic hydrocarbon group represented by Ra is the Ar in the compound represented by formula (6) described later. 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 Examples of similar aromatic hydrocarbon groups include, but are not particularly limited, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, spirofluorenyl, pyrenyl, fluoranthenyl, triphenylenyl, tetracenyl, and chrysenyl groups, and it is preferable that they have at least one of the aforementioned electron acceptor sites as substituents.

[0046] In formulas (2-1) to (2-7), the heteroaromatic group represented by Ra may be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. The heteroaromatic group represented by Ra may be in the compound represented by formula (6) described later, with Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 Similar heteroaromatic groups include nitrogen-containing heteroaromatic groups, oxygen-containing heteroaromatic groups, and sulfur-containing heteroaromatic groups, with nitrogen-containing heteroaromatic groups being preferred. Specific examples include pyridyl groups, pyrimidyl groups, pyrazyl groups, triazinyl groups, etc., which may be linked rings formed by the linkage of 2-3 monorings, and which preferably have at least one of the aforementioned electron acceptor sites as substituents.

[0047] In formulas (2-1) to (2-7), at least one of Ra is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heteroaromatic group, wherein the aromatic hydrocarbon group or heteroaromatic group is a monoring, or a linking ring or fused ring containing multiple rings, where the monorings constituting the linking ring may consist only of monorings of aromatic hydrocarbon groups, only of monorings of heteroaromatic groups, or a linking ring combining a monoring of an aromatic hydrocarbon group and a monoring of a heteroaromatic group, and the number of monorings constituting the linking ring may be 2 to 8. The linking ring may be a linking ring in which monorings are linked in a straight chain, or a linking ring that is linked so as to branch from one monoring.

[0048] In formula (2-9), examples of adjacent groups that bond to the binding site represented by * include phenyl groups, naphthyl groups, phenanthryl groups, dimethylfluorenyl groups, diphenylfluorenyl groups, diphenylspirobiofluorenyl groups, and pyridyl groups.

[0049] The structures of formulas (2-1) to (2-9) have a tetrahedral stereochemical region (2), which strengthens the binding of chemical bonds and intermolecular interactions in the material (1) for the photoelectric conversion element of an image sensor. This provides a novel compound and material for the photoelectric conversion element of an image sensor with a very high glass transition temperature and heat resistance. The novel compound and material for the photoelectric conversion element of an image sensor with a very high glass transition temperature and heat resistance can increase the process temperature in the image sensor fabrication process and the operating temperature range of the image sensor. The molecular weight of the material (1) for the photoelectric conversion element of an image sensor having the stereochemical region (2) is 500 or more.

[0050] The material (1) for the photoelectric conversion element for the image sensor has at least one stereostructure represented by the following formulas (2-1) to (2-9), and more preferably it is a compound having at least one substituent on the electron acceptor site.

[0051] The following are some preferred examples of photoelectric conversion element materials for image sensors included in a layer of a photoelectric conversion element according to one aspect of the present invention, but the present invention is not limited to these.

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[0113] [Compound represented by formula (6)] In one aspect of the present invention, the material (1) for a photoelectric conversion element for an imaging device described above may be a compound represented by the following formula (6). The compound represented by formula (6) also falls within the scope of the present invention. ​ In the above formula (6), Ar 1 ~Ar 3 each independently represents 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 cycloaliphatic hydrocarbon group; L 1 ~L 3 each independently represents a substituted or unsubstituted divalent to tetravalent aromatic hydrocarbon group, a substituted or unsubstituted divalent to tetravalent heteroaromatic group, or a substituted or unsubstituted divalent to tetravalent cycloaliphatic hydrocarbon group; The number of carbon atoms in the aromatic hydrocarbon group is 6 to 28; The number of carbon atoms in the heteroaromatic group is 3 to 二十四; The number of carbon atoms in the cycloaliphatic hydrocarbon group is 10 to 16; a 1 、a 2 、b 1 、b 2 、c 1 、and c 2 each independently represents an integer of 1 to 3; p, q and r each independently represent an integer of 0 to 3; Ar 1 、Ar 2 、and Ar 3 at least one of them is a group represented by formula (2-8-1);

Chemical formula

[0114] Ar 1 ~Ar 3 The number of carbon atoms in each is preferably 5 to 50, more preferably 5 to 30, and even more preferably 6 to 26. 1 ~Ar 3 By having a larger number of carbon atoms within the above range, the thermal stability of the layers in the image sensor can be further enhanced. 1 ~Ar 3 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 further increased, and the ease of manufacturing the material for the photoelectric conversion element of the image sensor can be further increased. Thus, Ar 1 ~Ar 3 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.

[0115] Ar 1 ~Ar 3 The aromatic hydrocarbon group represented by can be a monocyclic ring, a linked ring containing multiple rings, or a fused ring. Examples of aromatic hydrocarbon groups are not limited to phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, pyrenyl, fluoranthenyl, triphenylenyl, tetracenyl, triptycenyl, and chrysenyl groups.

[0116] Ar 1 ~Ar 3The heteroaromatic group represented by is not particularly limited, but for example, it is a functional group that contains a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, and / or 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 the same or different from each other.

[0117] Examples of nitrogen-containing heteroaromatic groups include heteroaromatic monocyclic groups such as pyridyl, pyrimidyl, pyrazyl, triazinyl, tetradinyl, and imidazolyl groups, as well as quinolyl, isoquinolyl, quinoxalyl, azaanthryl, diazaanthryl, triazaanthryl, tetraazaanthryl, azaphenanthryl, diazaphenanthryl, triazaphenanthryl, tetraazaphenanthryl, azapyrenyl, diazapyrenyl, triazapyrenyl, tetraazapyrenyl, azafluoranthenyl, and diazaph Examples include fused rings of heteroaromatic monocyclic groups such as ruolanthenyl group, triazafluoranthenyl group, tetraazafluoranthenyl group, azatriphenylenyl group, diazatriphenylenyl group, triazatriphenylenyl group, tetraazatriphenylenyl group, pentaazatriphenylenyl group, hexaazatriphenylenyl group, oxazolyl group, pyrrolyl group, imidazolyl group, triazolyl group, thiadiazolyl group, oxadiazolyl group, benzothiazolyl group, benzoxazolyl group, benzothiadiazolyl group, and benzoxadiazolyl group.

[0118] Examples of oxygen-containing heteroaromatic groups include heteroaromatic monocyclic groups such as the furyl group, benzofuryl group, dibenzofuryl group, benzonaphthofuryl group, xanthenyl group, dibenzodioxynyl group, fluorenonyl group, and benzoxadiazolyl group, which are fused rings of heteroaromatic monocyclic groups.

[0119] Examples of sulfur-containing heteroaromatic groups include heteroaromatic monocycles such as thienyl groups, benzothienyl groups, dibenzothienyl groups, thioxanthenyl groups, and fused rings of heteroaromatic monocycles such as thianthrenyl groups.

[0120] Ar 1 ~Ar 3 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, it is preferable that the group has a stereomole (2), such as an adamantyl or diamantyl group having 10 or more carbon atoms.

[0121] Ar 1 ~Ar 3 In this, 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).

[0122] Ar 1 ~Ar 3Examples of being substituted with -P(=O)(Ar’)2 include groups having a steric moiety (2) such as a triphenylphosphine oxide group, a diphenylnaphthylphosphine oxide group, a diphenylphenanthrylphosphine oxide group, a diphenyl(dimethylfluorenyl)phosphine oxide group, a diphenyl(diphenylfluorenyl)phosphine oxide group, and a diphenylspirobifluorenylphosphine oxide group.

[0123] Also, Ar 1 ~Ar 3 Examples of the group substituted with -S(=O)2Ar’ include groups having a steric moiety (2) such as a diphenylsulfone group and a dibenzothiophene-5,5-dioxide group, and these can be a form of an aromatic group having at least one sulfone group and having 6 to 26 carbon atoms.

[0124] a 1 、a 2 、b 1 、b 2 、c 1 、and c 2 each independently represents an integer of 1 to 3, preferably an integer of 1 or 2. The material for a photoelectric conversion element for an imaging device shown in formula (1) has a 1 、a 2 、b 1 、b 2 、c 1 、and c 2 By optimizing each within such a range, it is possible to suppress a decrease in the glass transition temperature (T g ) of the material for a photoelectric conversion element for an imaging device, deepen the LUMO level of the material for a photoelectric conversion element for an imaging device, and increase the response speed in a photoelectric conversion element for an imaging device.

[0125] When the compound, which is a material for a photoelectric conversion element for an imaging device, shown in formula (6) has a plurality of Ar 1 、Ar 2 and Ar 3 respectively, each of Ar 1 、each of Ar 2 、each of Ar3 Each of them may be the same or different, and it is preferable that they are the same from the viewpoint of ease of manufacture.

[0126] <L 1 、L 2 、L 3 > In formula (6), L 1 、L 2 、and L 3 each independently represents a divalent to tetravalent aromatic hydrocarbon group, a divalent to tetravalent heteroaromatic group, or a divalent to tetravalent hydrocarbon group.

[0127] L 1 ~L 3 The aromatic hydrocarbon group represented by may be a monocyclic, or a linked ring or condensed ring containing a plurality of rings. The aromatic hydrocarbon group is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluorenyl group, a dimethylfluorenyl group, a spirofluorenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a tetracenyl group, and a chrysenyl group.

[0128] L 1 ~L 3 The heteroaromatic group represented by is not particularly limited, and is, for example, a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and / or a germanium atom as a heteroatom on an aromatic ring, and may be a monocyclic, or a linked ring or condensed ring containing a plurality of rings. Examples of the heteroaromatic group include, for example, the nitrogen-containing heteroaromatic group, oxygen-containing heteroaromatic group, and sulfur-containing heteroaromatic group exemplified for the above-mentioned Ar 1 ~Ar 3 Among them, a nitrogen-containing heteroaromatic group is preferable, and specific examples thereof include a pyridyl group, a pyrimidyl group, a pyrazyl group, a triazinyl group, and the like.

[0129] L 1 ~L 3 Examples of the hydrocarbon group represented by include, for example, Ar 1 ~Ar 3Similarly, cyclic aliphatic hydrocarbon groups having 10 or more carbon atoms, such as those exemplified by the above-mentioned adamantyl group, can be mentioned.

[0130] L 1 ~L 3 In L 1 ~L 3 , the aromatic hydrocarbon group, heteroaromatic group, and hydrocarbon group may each independently have a substituent or may not have a substituent. In other words, the aromatic hydrocarbon group, heteroaromatic group, and hydrocarbon group are either substituted or unsubstituted. Specific examples of the substituents that these functional groups can have are the same as the specific examples of the substituents that Ar

[0131] p, q, and r each independently represent an integer from 0 to 3, preferably an integer from 0 to 2. By optimizing p, q, and r within such ranges for the material for a photoelectric conversion element for an imaging device shown in formula (6), it is possible to suppress the decrease in T g of the material for a photoelectric conversion element for an imaging device, deepen the LUMO level of the material for a photoelectric conversion element for an imaging device, and increase the response speed in the imaging device. When p is 0, L 1 represents a single bond. Therefore, in formula (6), Ar 1 is directly bonded to the triazine ring by a single bond. Similarly, when q and r are each 0, L 2 and L 3 each represent a single bond.

[0132] When the compound, which is a material for a photoelectric conversion element for an imaging device shown in formula (6), has a plurality of L 1 , L 2 , and L 3 respectively, each of L 1 , each of L 2 , and each of L 3 may be the same or different from each other.

[0133] <Characteristics of Ar, L, and Triazine Ring> Ar 1 Ar 2 and Ar3 At least one of them is expressed by equation (2-8-1);

[0134] [ka]

[0135] In the above equation (2-8-1), * indicates a bonding site with an adjacent group.

[0136] In that the glass transition temperature of the compound represented by formula (6) is increased, the Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 Preferably, at least one of them is a structure represented by formula (2-8-1).

[0137] Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 In these groups, the sum of the number of cyano groups, adamantyl groups, or groups represented by formula (2-8-1) is 2 or more. In other words, the compound represented by formula (6) has at least one group represented by formula (2-8-1), in addition to Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 At least one of them satisfies at least one of the following conditions (i) to (viii). (i) Substituted with a cyano group. (ii) Substituted with a group having a cyano group (iii) It is an adamantyl group. (iv) Substituted with an adamantyl group. (v) Substituted with a group containing an adamantyl group. (vi) It is a base represented by equation (2-8-1). (vii) It is substituted with the base represented by formula (2-8-1). (viii) It is substituted with a group having the group represented by formula (2-8-1).

[0138] That is, for example, in the following compound (D-60), Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 The sum of the number of adamantyl groups in, or the number of groups represented by formula (2-8-1), is 2.

[0139] [ka]

[0140] Furthermore, for example, in the following compound (D-145), Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 The sum of the number of bases represented by equation (2-8-1) in this case is 2.

[0141] [ka]

[0142] Furthermore, for example, in the following compound (D-27), Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 The sum of the number of cyano groups in compound (D-27), or the number of groups represented by formula (2-8-1), is 3. That is, in the isophthalonitrile group of compound (D-27), there are 2 cyano groups per group.

[0143] [ka]

[0144] Ar 1 Ar 2 Ar 3 , L 1 , L 2 and L 3 If at least one of these compounds has such characteristics, a novel compound and material for a photoelectric conversion element for an image sensor is provided that has a very high glass transition temperature and heat resistance, which can deepen the LUMO level of the photoelectric conversion element material for an image sensor and increase the response speed in the image sensor.

[0145] Preferred specific examples of compounds represented by formula (6) are shown below, but the present invention is not limited to these.

[0146] [ka]

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174] [ka]

[0175] [ka]

[0176] Furthermore, the material for the photoelectric conversion element for an image sensor, the material for the photoelectric conversion element for an image sensor (1), and the compound represented by formula (6) according to one aspect of the present invention can be synthesized by appropriately combining known reactions (for example, the Suzuki-Miyaura cross-coupling reaction).

[0177] <Materials for photoelectric conversion elements in image sensors, hole block materials for image sensors> A material (1) for a photoelectric conversion element for an image sensor according to one aspect of the present invention comprises a compound (for example, a compound having a stereochemical structure represented by formulas (2-1) to (2-9)) having a stereochemical region (2) having a stereochemical region formed such that adjacent atoms bonded to a central atom (3) are arranged at the vertices of a tetrahedron, and having at least one first cyclic structure including the central atom (3) of the stereochemical region (2), and having at least one second cyclic structure including at least one atom in the first cyclic structure, or a compound that partially contains the stereochemical region (2). The applications of the image sensor material 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.

[0178] Furthermore, the material for the photoelectric conversion element for an image sensor according to one aspect of the present invention has high T gBy having this, changes in the film state such as crystallization due to annealing during the production of the photoelectric conversion element are prevented. As a result, a decrease in the external quantum efficiency in the imaging device formed from the material for a photoelectric conversion element for an imaging device according to one aspect of the present invention is prevented, and the dark current is reduced. Therefore, the material for a photoelectric conversion element for an imaging device according to one aspect of the present invention can be suitably used as a material for a photoelectric conversion element of an imaging device and a hole-blocking material, which requires resistance to annealing after forming the photoelectric conversion layer.

[0179] The material for a photoelectric conversion element for an imaging device according to one aspect of the present invention can be used, for example, as a hole-blocking material that is a material for a photoelectric conversion layer or a material for a hole-blocking layer in the imaging device in the imaging device.

[0180] The material for a photoelectric conversion element for an imaging device according to one aspect of the present invention includes a skeleton represented by the above three-dimensional site (2). The material for a photoelectric conversion element for an imaging device and the hole-blocking material including the skeleton represented by the three-dimensional site (2) contribute to the production of a material for a photoelectric conversion element for an imaging device excellent in response speed and external quantum efficiency characteristics.

[0181] <Regarding the LUMO level> For photoelectric conversion elements used in image sensors, it may be necessary to rapidly transfer the charge generated in the photoelectric conversion layer in order to reduce dark current, improve external quantum efficiency, and improve response speed. For rapid charge transfer, it is preferable that the LUMO levels of the n-type semiconductor material in the photoelectric conversion layer and the material used in the hole block layer are close. For example, when using fullerene (C60) in the photoelectric conversion layer, it is more preferable that the LUMO levels of the hole block layer, as quantum chemical calculation values ​​obtained by density functional theory (DFT) as described later, be -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, and -3.0 eV or less. Furthermore, the LUMO level of the hole block layer is not limited, but it should be -5.0 eV or higher, and preferably -4.0 eV or higher.

[0182] In an image sensor according to one aspect of the present invention, the LUMO level of the material for the photoelectric conversion element of the image sensor is a numerical value calculated by quantum chemical calculations, and the optimization of the molecular structure and the calculation of the LUMO level can be obtained using density functional theory (DFT) with the calculation conditions of the B3LYP functional and the 6-31G(d) basis function using a Gaussian program.

[0183] <About glass transition temperature> The glass transition temperature of the material for the photoelectric conversion element for the image sensor used to form the layer of the image sensor according to one aspect of the present invention is not particularly limited, but from the viewpoint of suitability to the image sensor, i.e., the photoelectric conversion element for the image sensor, it is preferable that the glass transition temperature is 130°C or higher, more preferably 140°C or higher, more preferably 150°C or higher, and more preferably 160°C or higher. This glass transition temperature is a value obtained from differential scanning calorimetry.

[0184] The differential scanning calorimeter and test conditions are as follows: Differential scanning calorimeter model: Hitachi High-Tech DSC7020; Operating conditions: The glass transition temperature was determined from the peak obtained after two scans under the conditions of heating rate of 10°C / min and temperature range of 40°C to 400°C.

[0185] <Regarding amorphous properties> In one aspect of the present invention, the photoelectric conversion element material (1) for an image sensor, preferably the photoelectric conversion element material for an image sensor represented by formulas (2-1) to (2-9) and the compound represented by formula (6), is preferably such that the deposited film of the material forms an amorphous layer. If the deposited film is a crystalline layer, the interface with adjacent layers will not be uniform, which can lead to defects in the element.

[0186] There are no particular limitations on how to determine whether a deposited film is an amorphous layer or not, but it can be determined by methods commonly used by those skilled in the art, such as visual inspection to determine the presence or absence of crystallization, or by XRD measurement of the deposited film, where no sharp diffraction peaks are observed.

[0187] <Image sensor> An image sensor according to one aspect of the present invention, comprising a layer containing a material for a photoelectric conversion element for an image sensor according to one aspect of the present invention.

[0188] The configuration of the image sensor is not particularly limited, but for example, the following configurations (i) to (vi) can be considered.

[0189] (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

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] [Layer containing materials for photoelectric conversion elements in image sensors] An image sensor, which is one embodiment of a photoelectric conversion element, may contain, 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, the photoelectric conversion element material (1) for image sensors according to the above embodiment of the present invention, preferably the photoelectric conversion element material for image sensors represented by formulas (2-1) to (2-9), or a compound represented by formula (6). In the example configuration shown in Figure 1, the image sensor 100 contains the photoelectric conversion element material for image sensors in at least one layer selected from the group consisting of a hole block layer 2 and a photoelectric conversion layer 3. In an image sensor according to one embodiment of the present invention, it is preferable that the hole block layer 2 contains the photoelectric conversion element material for image sensors. This has the effect of rapidly moving the necessary charge while controlling the reverse movement of holes.

[0197] Furthermore, the photoelectric conversion element material (1) for an image sensor, preferably the photoelectric conversion element material for an image sensor represented by formulas (2-1) to (2-9), or the compound represented by formula (6) (photoelectric conversion element material for an image sensor), as described above in one aspect of the present invention, may be included in a plurality of 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 an image sensor.

[0198] The following describes an imaging photoelectric conversion element 100 in which the hole block layer 2 contains a material for photoelectric conversion elements.

[0199] [First electrode 1] A first electrode 1 is provided on the substrate.

[0200] 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.

[0201] 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.

[0202] 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 sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, silver, gold, magnesium / silver mixture, aluminum, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, iridium, molybdenum, palladium, platinum, and rare earth metals.

[0203] [Hole Block Layer 2] A hole blocking layer 2 is provided between the first electrode 1 and the photoelectric conversion layer 3, which is a light-receiving layer and will be described later.

[0204] 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.

[0205] 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 (1) for an image sensor according to one aspect of the present invention described above, preferably a photoelectric conversion element material for an image sensor represented by formulas (2-1) to (2-9), or a compound represented by formula (6) (photoelectric conversion element material for an image sensor). 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.

[0206] 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.

[0207] [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.

[0208] 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).

[0209] Materials used in the photoelectric conversion layer 3 include n-type semiconductors and p-type semiconductors. N-type semiconductors are acceptor-type organic semiconductors, and compounds that readily accept electrons and have high electron transport properties are used. P-type semiconductors are donor-type organic semiconductors, and compounds that readily donate electrons and have high hole transport properties are used. When multiple materials are used in the photoelectric conversion layer 3, possible combinations include, for example, an n-type semiconductor and a p-type semiconductor, an n-type semiconductor and a compound with lower acceptor properties than the n-type semiconductor, and a p-type semiconductor and a compound with lower donor properties than the p-type semiconductor. Each material may be used individually, or two or more materials may be used. The photoelectric conversion layer 3 may contain a dye compound that is excellent at absorbing specific light. The dye compound may be a compound with lower acceptor properties than the n-type semiconductor, or a compound with lower donor properties than the p-type semiconductor. In terms of increasing photoelectric conversion efficiency, it is desirable that the photoelectric conversion layer 3 contains a dye compound in addition to the n-type and p-type semiconductors. Examples of compounds included in the photoelectric conversion layer 3 include coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, fullerene and its derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, oxazole, oxadiazole, and triazole, naphthalenetetracarboxylic acid diimide, and hole transport materials. The photoelectric conversion layer 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.

[0210] Specific examples of coumarin derivatives include coumarin 6 and coumarin 30. Specific examples of quinacridone derivatives include N,N-dimethylquinacridone. Specific examples of phthalocyanine derivatives include boron subphthalocyanine chloride, boron subnaphthalocyanine chloride (SubNC), F6-SubPC-OC6F5, and Cl6-SubPC-OC6.

[0211] Specific examples of fullerenes and their derivatives include

[60] fullerene,

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

[60] PCBM).

[0212] 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, benzothienobenzothiophene 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.

[0213] 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).

[0214] [ka]

[0215] 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).

[0216] [Electronic Block Layer 4] An electron blocking layer 4 is provided between the photoelectric conversion layer 3 and the hole transport layer 5.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] [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.

[0221] The hole transport layer 5 may be a known material, for example, naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA) or its derivatives, or aromatic compounds having a cyano group such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN).

[0222] 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. A conventionally known hole transport material is an example, the same as the one used in the photoelectric conversion layer 3 described above.

[0223] [Second electrode 6] A second electrode 6 is provided on the hole transport layer 5.

[0224] Examples of materials for the second electrode 6 include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, aluminum, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, silver, gold, molybdenum, palladium, platinum, and rare earth metals. In the case of a photoelectric conversion element for an image sensor in which light is incident on the photoelectric conversion layer from the second electrode 6 side, the material constituting the second electrode 6 may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide, etc.

[0225] [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).

[0226] 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.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 〔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, wherein the material for a photoelectric conversion element for an image sensor (1) has at least one tetrahedral stereoscopic portion (2), the tetrahedral stereoscopic portion (2) has a central atom (3) at the center of the tetrahedron, and at the vertices of the tetrahedron there are portions selected from a lone pair of electrons (4) of the central atom (3) and 3 or 4 adjacent atoms (5) bonded to the central atom (3), and further has a first cyclic structure and a second cyclic structure condensed to the first cyclic structure, the first cyclic structure comprising the central atom (3) and two of the adjacent atoms (5), and at least one substituted or unsubstituted aromatic hydrocarbon group or substituted or unsubstituted heteroaromatic group is linked to the first cyclic structure or the second cyclic structure, the aromatic hydrocarbon group or heteroaromatic group being a monoring or a linked ring or fused ring containing multiple rings.

[0231] In one aspect 2 of the present invention, the image sensor, in aspect 1, more preferably, has at least one of the three-dimensional structures represented by the following formulas (2-1) to (2-9), including the three-dimensional portion (2), the first annular structure, and the second annular structure;

[0232] [ka]

[0233] In the above equations (2-1) to (2-9), W 1 and W 2 Each of these independently represents either C-Ra or N; W 3 Each of these independently represents either C(-Ra)2 or N-Ra; Ra represents, either identical or distinct, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted hydrocarbon group, a hydrogen atom, a halogen atom, or a cyano group; * indicates a bonding site with an adjacent group; The stereostructures of formulas (2-1) to (2-9) may be unsubstituted or have substituents; The three-dimensional structures of equations (2-1) to (2-9) may be further connected to or fused with three-dimensional parts (2). At least one of the Ra is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heteroaromatic group, and the aromatic hydrocarbon group or heteroaromatic group is a monoring, a linking ring containing multiple rings, or a fused ring. The molecular weight of the material (1) for the photoelectric conversion element for the image sensor is more preferably 500 or more.

[0234] In the image sensor according to one embodiment 3 of the present invention, it is preferable that the glass transition temperature of the material (1) for the photoelectric conversion element for the image sensor is 140°C or higher, in embodiment 1 or 2.

[0235] In one aspect 4 of the present invention, the image sensor is more preferably such that the central atom (3) of the material (1) for the photoelectric conversion element of the image sensor is a carbon atom, a nitrogen atom, a silicon atom, a phosphorus atom, or a sulfur atom.

[0236] In one aspect 5 of the present invention, in aspect 1, it is more preferable that the first annular structure in the material (1) for the photoelectric conversion element for the image sensor, including the central atom (3) of the three-dimensional portion (2), is a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or an eight-membered ring.

[0237] In one aspect 6 of the present invention, the image sensor, in aspect 1, is more preferably such that the second annular structure in the material (1) for the photoelectric conversion element of the image sensor is a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or an 8-membered ring.

[0238] In one aspect 7 of the present invention, the image sensor is more preferably such that, in aspect 1, the glass transition temperature of the material (1) for the photoelectric conversion element of the image sensor is 140°C or higher; the central atom (3) in the material (1) for the photoelectric conversion element of the image sensor is a carbon atom, a nitrogen atom, a silicon atom, a phosphorus atom, or a sulfur atom; the first annular structure in the material (1) for the photoelectric conversion element of the image sensor is a five-membered ring or a six-membered ring; and the second annular structure in the material (1) for the photoelectric conversion element of the image sensor is a five-membered ring or a six-membered ring.

[0239] In one aspect 8 of the present invention, it is more preferable that the image sensor material (1) for the image sensor photoelectric conversion element has at least one electron acceptor portion in any of the above aspects 1 to 7.

[0240] The compound according to one aspect 9 of the present invention is It is preferable that the compound is represented by the following formula (6) and has a tetrahedral stereochemical moiety (2); [ka] In the above formula (6), Ar1 ~Ar 3 Each of these independently represents 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 1 ~L 3 Each of these independently represents a 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; The number of carbon atoms in the aforementioned aromatic hydrocarbon group is between 6 and 28; The number of carbon atoms in the aforementioned heteroaromatic group is 3 to 24; The number of carbon atoms in the cyclic aliphatic hydrocarbon group is 10 to 16; a 1 a 2 , b 1 , b 2 , c 1 , and c 2 Each of these independently represents an integer between 1 and 3; p, q, and r each independently represent integers between 0 and 3; Ar 1 Ar 2 , and Ar 3 At least one of them has a three-dimensional structure that includes a tetrahedron-shaped three-dimensional part (2) represented by formula (2-8-1); [ka] In the above equation (2-8-1), * indicates a bonding site with an adjacent group; Ar 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 In these groups, the sum of the number of cyano groups, adamantyl groups, or groups represented by formula (2-8-1) is 2 or more; The molecular weight of the compound represented by formula (6) should be 550 or greater.

[0241] A compound according to one aspect 10 of the present invention is, in aspect 9, the Ar in formula (6). 1 Ar 2 Ar 3 , L 1 , L 2 , and L 3 It is more preferable that at least one of these be expressed by formula (2-8-1).

[0242] A compound according to one aspect 11 of the present invention is, in aspect 9 or 10, a of formula (6) 1 a 2 , b 1 , b 2 , c 1 , and c 2 It is more preferable that each of these be an integer of 1 or 2, independently of the others.

[0243] In the compound according to one embodiment 12 of the present invention, it is more preferable that in any of embodiments 9 to 11, p, q, and r in formula (6) are each independently integers from 0 to 2.

[0244] A compound according to one embodiment 13 of the present invention is, in any of embodiments 9 to 12, the Ar in formula (6). 1 ~Ar 3 It is more preferable that each of these groups independently be a substituted or unsubstituted divalent to trivalent phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, triphenylenyl group, dibenzocrisenyl group, triazyl group, pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuryl group, benzothienyl group, dibenzofuryl group, or dibenzothienyl group.

[0245] A compound according to one aspect 14 of the present invention is, in any of the above aspects 9 to 13, L in formula (6). 1 ~L 3It is more preferable that each of these groups independently be a substituted or unsubstituted divalent to tetravalent phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, triphenylenyl group, dibenzocrisenyl group, triazyl group, pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuryl group, benzothienyl group, dibenzofuryl group, or dibenzothienyl group.

[0246] A material for a photoelectric conversion element for an image sensor according to one aspect 15 of the present invention contains a compound described in any of aspects 9 to 14.

[0247] In one aspect 16 of the present invention, it is more preferable that the material for the photoelectric conversion element for an image sensor in aspect 15 is a hole block material.

[0248] An image sensor according to one aspect 17 of the present invention comprises a layer containing a photoelectric conversion element material for an image sensor according to either aspect 15 or 16.

[0249] <Additional Notes> 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]

[0250] 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.

[0251] <Synthesis Example-1> 2-(4'-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)-[1,1'-biphenyl]-4-yl)dibenzothiophene-5,5-dioxide (A-960)

[0252] [ka]

[0253] Under an argon atmosphere, 2,4-di([1,1'-biphenyl]-4-yl)-6-(4'-chloro-[1,1'-biphenyl]-4-yl)-1,3,5-triazine (1.0 g, 1.7 mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzothiophene-5,5-dioxide (0.64 g, 1.9 mmol), palladium acetate (5.8 mg, 0.026 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (17 mg, 0.035 mmol) were suspended in tetrahydrofuran (18 mL). 2.6 mL, 5.2 mmol of 2 M tripotassium phosphate aqueous solution was added to this suspension, and the mixture was refluxed for 4 hours. After allowing the reaction solution to cool to room temperature, 9 mL of ethanol was added, and the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and washed with water, methanol, and hexane. The obtained solid was vacuum-dried, then suspended in 70 mL of toluene and 30 mL of pyridine, dissolved at 120°C, and then 0.1 g of activated carbon was added and the mixture was heated for another 15 minutes. This suspension was filtered through Celite, and the precipitated solid from the filtrate was filtered off and vacuum-dried. The obtained solid was purified by sublimation to obtain 2-(4'-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)-[1,1'-biphenyl]-4-yl)dibenzothiophene-5,5-dioxide (A-960) (yield 1.1 g, yield 80%).

[0254] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.86-8.83(m,6H),7.99(s,1H),7.91-7.79(m,11H),7.76-7.70(m ,7H),7.66(t,J=7.5Hz,1H),7.56(t,J=7.8Hz,1H),7.50(t,J=7.8Hz,4H),7.42(t,J=7.3Hz,2H).

[0255] <Synthesis Example-2> 2-(4-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)phenyl)dibenzothiophen-5,5-dioxide (A-396)

[0256] [ka]

[0257] Under an argon atmosphere, 2,4-di([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-1,3,5-triazine (1.0 g, 1.7 mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzothiophene-5,5-dioxide (0.64 g, 1.9 mmol), palladium acetate (5.8 mg, 0.026 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (17 mg, 0.035 mmol) were suspended in tetrahydrofuran (18 mL). 2.6 mL, 5.2 mmol, 2 M tripotassium phosphate aqueous solution was added to this suspension, and the mixture was refluxed for 5 hours. After the reaction solution cooled to room temperature, 17 mL of ethanol was added, and the mixture was stirred at room temperature for a further 15 hours. After filtering off the precipitated solid, it was washed with water, methanol, and hexane. The obtained solid was vacuum-dried, then suspended in 40 mL of toluene and 40 mL of pyridine, dissolved at 110°C, and then 0.2 g of activated carbon was added and heated for a further 15 minutes. This suspension was filtered through Celite, and the precipitated solid from the filtrate was filtered off and vacuum-dried. The obtained solid was purified by sublimation to obtain 2-(4-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)phenyl)dibenzothiophen-5,5-dioxide (A-396) (yield 1.6 g, yield 76%).

[0258] 1H-NMR(400MHz,CDCl3)δ(ppm):8.91(d,J=8.6Hz,2H),8.86(d,J=8.7Hz,4H),8.05(s,1H),7.94(d,J=7.8Hz,1H),7.92(d,J=7.8Hz,1 H),7.88(d,J=7.6Hz,1H),7.81-7.85(m,7H),7.73-7.67(m,5H),7.58(t,J=7.6Hz,1H),7.52(t,J=7.7Hz,4H),7.43(t,J=7.3Hz,2H).

[0259] <Synthesis Example-3> 2,4-di([1,1'-biphenyl]-4-yl)-6-(4'-(adamantan-1-yl)-5-(2-phenylpyridine)-3-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine(A-952)

[0260] [ka]

[0261] Under an argon atmosphere, 2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (1.4 g, 3.3 mmol), 3-(4'-(adamantan-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-yl)-2-phenylpyridine (2.0 g, 3.5 mmol), and tetrakis(triphenylphosphine)palladium (0.12 g, 0.010 mmol) were suspended in THF (33 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 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 off to obtain 2,4-di([1,1'-biphenyl]-4-yl)-6-(4'-(adamantan-1-yl)-5-(2-phenylpyridine)-3-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine (A-952) (1.8g, 65%).

[0262] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.92(dd,J=1.6,1.6Hz,1H),8.83(brd,J=8.5Hz,4H),8.79( dd,J=4.8,1.7Hz,1H),8.68(dd,J=1.6,1.6Hz,1H),8.00(dd,J=7.9,1.7Hz,1H),7.83(brd, J=8.5Hz,4H),7.73(brd,J=7.4Hz,4H),7.58(dd,J=1.6.1.6Hz,1H),7.55-7.49(m,6H),7.4 9-7.40(m,7H),7.37-7.29(m,3H),2.17-2.11(m,3H),2.00-1.96(m,6H),1.87-1.74(m,6H).

[0263] <Synthesis Example-4> 2-(4-(adamantan-1-yl)phenyl)-4,6-bis(4-(2-phenylpyridine-3-yl)phenyl)-1,3,5-triazine(A-918)

[0264] [ka]

[0265] Under an argon atmosphere, 2-(4-(-adamantan-1-yl)phenyl)-4,6-bis(4-chlorophenyl)-1,3,5-triazine (1.5 g, 2.9 mmol), 2-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (1.8 g, 6.5 mmol), palladium acetate (33 mg, 0.15 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.014 g, 0.29 mmol) were suspended in THF (30 mL). 2M potassium carbonate aqueous solution (10 mL, 20 mmol) was added to this suspension, and the mixture was refluxed for 17 hours. Water was added to the reaction solution, and the mixture was extracted with toluene. The organic layer was washed with water. The organic layer was separated, sodium sulfate and activated carbon were added, and the mixture was stirred. After filtration with Celite, the solvent was removed by distillation. The obtained solid was washed with hot octane and hot ethanol to obtain 2-(4-(adamantan-1-yl)phenyl)-4,6-bis(4-(2-phenylpyridine-3-yl)phenyl)-1,3,5-triazine (A-918) (1.7g, 77%).

[0266] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.75(dd,J=4.8,1.6Hz,2H),8.67(brd,J=8.4Hz,4H),8.66(brd,J=8.6Hz,2H),7.82(dd,J=7.7,1.7 Hz,2H),7.55(brd,J=8.6Hz,2H),7.44-7.37(m,10H),7.29-7.24(m,6H),2.18-2.11(m,3H),2.03-1.95(m,6H),1.88-1.76(m,6H).

[0267] <Synthesis Example-5> 2-(3-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)phenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine(A-942)

[0268] [ka]

[0269] (Step 1) 2-(3-bromophenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine(X32) Under an argon atmosphere, 3-bromobenzoyl chloride (X31) (3.3 mL, 25 mmol) and isonicotinamide hydrochloride (12 g, 75 mmol) were suspended in xylene (250 mL). Triethylamine (11 mL, 75 mmol) was added to this suspension at room temperature, and the mixture was stirred at room temperature for 2 minutes and then at 60°C for 20 minutes. 1,1,3,3-tetramethyldisiloxane (13 mL, 75 mmol) was then added, and the mixture was stirred at 150°C for 12 hours, after which the low-boiling fraction was removed under reduced pressure. The resulting solid was washed with water, methanol, hexane, and a small amount of acetone to obtain 2-(3-bromophenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine (X32) (yield 3.7 g, yield 38%).

[0270] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.93(brdd,J=6.1,1.6Hz,4H),8.89(brdd,J=1.8,1.8Hz,1H),8.71(brd ,J=8.0Hz,1H),8.56(brdd,J=6.1,1.6Hz,4H),7.80(brd,J=8.0Hz,1H),7.50(brdd,J=7.9,7.9Hz,1H).

[0271] (Step 2) 2-(3-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)phenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine(A-942) Under an argon atmosphere, 2-(3-bromophenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine (X32) (2.7 g, 7.0 mmol), 2-(9,10-dihydro-9,10[1,2]-benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (2.5 g, 6.6 mmol), palladium acetate (79 mg, 0.35 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (334 mg, 0.70 mmol) were suspended in THF (70 mL). 2M potassium carbonate aqueous solution (14 mL, 28 mmol) was added to this suspension, and the mixture was stirred at 80°C for 2 hours. Next, 2-(9,10-dihydro-9,10[1,2]-benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (692 mg, 1.8 mmol) was added, and the mixture was heated and stirred at 80°C for 13 hours. After cooling to room temperature, chloroform and water were added to the reaction mixture, and the organic layer was extracted. Sodium sulfate and activated carbon were added to the organic layer and stirred, and then the mixture was filtered by Celite filtration. Furthermore, medium-pressure column chromatography using silica gel (100% hexane, followed by hexane:chloroform = 50:50, followed by 100% chloroform) was performed, followed by washing with hot toluene, and then washing with hexane, methanol, and a small amount of acetone to obtain 2-(3-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)phenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine (A-942) (yield 1.6 g, yield 41%).

[0272] 1H-NMR(400MHz,CDCl3)δ(ppm):8.91(brdd,J=6.1,1.6Hz,4H),8.85(brdd,J=1.6,1.6Hz ,1H),8.70(brd,J=7.8Hz,1H),8.54(brdd,J=6.1,1.6Hz,4H),7.77(brdd,J=6.1,1.6Hz ,1H),7.72(d,J=1.5Hz,1H),7.62(brdd,J=7.7,7.7Hz,1H),7.54(d,J=7.6Hz,1H),7.48 -7.42(m,4H),7.33(dd,J=7.6,1.7Hz,1H),7.06-7.02(m,4H),5.57(s,1H),5.53(s,1H).

[0273] <Synthesis Example-6> 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)-pyridine-3-yl)phenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine(A-944)

[0274] [ka]

[0275] (Step 1) 5-Chloro-2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)pyridine (X42) Under an argon atmosphere, 2-(9,10-dihydro-9,10[1,2]-benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (13 g, 33.8 mmol), 2-bromo-5-chloropyridine (9.8 g, 26 mmol), and tetrakis(triphenylphosphine)palladium (2.5 g, 2.2 mmol) were suspended in THF (70 mL). 2M potassium carbonate aqueous solution (50 mL, 0.10 mol) was added to this suspension, and the mixture was stirred at 80°C for 42 hours. After cooling to room temperature, chloroform and water were added to the reaction mixture, and the organic layer was extracted. The organic layer was then washed with saturated brine. Sodium sulfate and activated carbon were added to the organic layer and stirred. The mixture was then filtered by Celite filtration, and the low-boiling fraction was removed under reduced pressure. The obtained solid was purified by column chromatography (hexane:chloroform = 100:0 to 50:50) to obtain 5-chloro-2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)pyridine (X42) (yield 6.3g, yield 66%).

[0276] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.58(dd,J=2.5,0.7Hz,1H),8.04(d,J=1.7Hz,1H),7.66(dd,J=8.5,2.5Hz,1H),7.59(dd,J=8.6, 0.7Hz,1H),7.54(dd,J=7.6,1.8Hz,1H),7.46(d,J=7.7Hz,1H),7.42-7.37(m,4H),7.02-6.98(m,4H),5.51(s,1H),5.47(s,1H).

[0277] (Step 2) 2-(9,10-dihydro-9,10-[1,2]-benzenoanthracene)-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)pyridine (X43) Under an argon atmosphere, 5-chloro-2-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)pyridine (X42) (5.76 g, 15.7 mmol), bis(pinacolato)diborone (4.51 g, 17.7 mmol), palladium acetate (0.18 g, 0.80 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.77 g, 1.6 mmol), and potassium acetate (5.6 g, 57 mmol) were suspended in xylene (100 mL) and stirred at 140 °C for 23 hours. After cooling to room temperature, chloroform and water were added to the reaction mixture, and the organic layer was extracted and then washed with saturated brine. Sodium sulfate and activated carbon were added to the organic layer and stirred, then Celite filtration was performed, and the low-boiling fraction was removed under reduced pressure to obtain 2-(9,10-dihydro-9,10-[1,2]-benzenoanthracene)-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)pyridine (X43) (crude yield 8.2 g, crude yield quant.). This crude product was used in the next reaction without purification.

[0278] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.96(dd,J=1.7,1.0Hz,1H),8.12(d,J=1.6Hz,1H),8.06(dd,J=8.0,1.8Hz,1H),7.63(d,J=7.8Hz, 1H),7.60(d,J=7.6Hz,1H),7.46(d,J=7.7Hz,1H),7.40-7.38(m,4H),7.01-6.97(m,4H),5.52(s,1H),5.47(s,1H),1.35(s,12H).

[0279] (Step 3) 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)-pyridine-3-yl)phenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine(A-944) Under an argon atmosphere, 2-(9,10-dihydro-9,10-[1,2]-benzenoanthracene-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)pyridine (X43) (2.5 g, 5.5 mmol), 2-(3-bromophenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine (X32) (1.9 g, 4.9 mmol), and tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol) were suspended in xylene (55 mL). 4M potassium phosphate aqueous solution (5.0 mL, 20 mmol) was added to this suspension, and the mixture was stirred at 130°C for 20 hours. After cooling to room temperature, water and methanol were added to the reaction mixture, and the precipitate was collected by filtration. The filter extract was suspended in DMF (300 mL), aerated with air at 140°C for 1.5 hours, and then filtered by Celite. The low-boiling fraction was removed under reduced pressure, and water and methanol were added to collect the precipitate by filtration. The filter extract was suspended in toluene (150 mL), heated to 120°C, and then filtered by hot Celite. Subsequently, the low-boiling fraction was concentrated under reduced pressure and washed with methanol to obtain 2-(3-(6-(9,10-dihydro-9,10-[1,2]-benzenoanthracen-2-yl)-pyridine-3-yl)phenyl)-4,6-bis(pyridine-4-yl)-1,3,5-triazine (A-944) (yield 1.3 g, yield 40%).

[0280] 1H-NMR(400MHz,CDCl3)δ(ppm):9.06(brd,J=1.9Hz,1H),9.03(brdd,J=1.6,1.6Hz,1H),8.93(brdd,J=6.1,1 .6Hz,4H),8.80(brd,J=7.8Hz,1H),8.57(brdd,J=6.1,1.6Hz,4H),8.19(brd,J=1.6Hz,1H),8.06(dd,J=8.3 ,1.6Hz,1H),7.92(brd,J=7.7Hz,1H),7.83(dd,J=8.3,0.6Hz,1H),7.74(brdd,J=7.9,7.9Hz,1H),7.69(brd ,J=7.7,1.7Hz,1H)7.52(brd,J=7.7Hz,1H)7.45-7.41(m,4H),7.04-7.00(m,4H),5.56(s,1H),5.51(s,1H).

[0281] <Synthesis Example-7> 4,6-Bis(biphenyl-4-yl)-2-[4'-(1-adamantyl)-5-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazine(A-949)

[0282] [ka]

[0283] Under an argon atmosphere, 4,6-bis(biphenyl-4-yl)-2-[3-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine (1.5 g, 2.3 mmol), 4-(1-adamantyl)phenyl triflate (1.2 g, 3.4 mmol), palladium acetate (5.1 mg, 0.023 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (22 mg, 0.045 mmol), and potassium carbonate (0.81 g, 5.9 mmol) were suspended in a mixed solvent of tetrahydrofuran (75 mL) and water (6 mL), and heated to 70 °C and stirred for 17 hours. After cooling to room temperature, water (50 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by silica gel chromatography (eluent: a 1:2 mixed solvent of chloroform and hexane) and recrystallization with toluene to obtain the target product, 4,6-bis(biphenyl-4-yl)-2-[4'-(1-adamantyl)-5-(3-pyridyl)biphenyl-3-yl]-1,3,5-triazine (A-949), as a white solid (yield 0.97 g, yield 57%).

[0284] 1 H-NMR(400MHz,CDCl3)δ(ppm):9.07(d,J=1.7Hz,1H),9.05(t,J=1.6Hz,1H),8.95(t,J=1.6H z,1H),8.86(d,J=8.6Hz,4H),8.68(dd,J=4.9Hz,1.6Hz,1H),8.08(ddd,J=1.7Hz,2.3Hz,7.9H z,1H),8.00(t,J=1.8Hz,1H),7.81(d,J=8.5Hz,4H),7.76(d,J=8.5Hz,2H),7.71(d,J=7.0Hz, 4H),7.55(d,J=8.5Hz,2H),7.52-7.39(m,7H),2.14(brs,3H),2.01(brs,6H),1.81(brs,6H).

[0285] <Synthesis Example-8> 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2-yl)phenyl)-6-phenyl-1,3,5-triazine-2-yl)picolinonitrile (A-955)

[0286] [ka]

[0287] Under an argon atmosphere, 5-(4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine-2-yl)picolinonitrile (2.0 g, 5.4 mmol), 2-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.3 g, 6.0 mmol), palladium acetate (36 mg, 0.16 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.16 g, 0.33 mmol) were suspended in THF (53 mL). 2M potassium carbonate aqueous solution (9.0 mL, 18 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 obtained solid was dissolved in toluene heated to 110°C and filtered while hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered to obtain 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)phenyl)-6-phenyl-1,3,5-triazine-2-yl)picolinonitrile (A-955) (yield 2.2g, yield 69%).

[0288] 1H-NMR(400MHz,CDCl3)δ(ppm):10.02(brd,J=2.0Hz,1H),9.14(dd,J=8.0,2.0H z,1H),8.77(brd,J=8.5Hz,4H),7.92(brd,J=8.0Hz,1H),7.76-7.71(m,3H),7. 67(brt,J=7.0Hz,1H),7.64-7.58(m,2H),7.51(d,J=7.7Hz,1H),7.47-7.40(m, 4H),7.34(dd,J=7.7,1.8Hz,1H),7.06-7.00(m,4H),5.55(s,1H),5.50(s,1H).

[0289] <Synthesis Example-9> 5,5'-((6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))dipicolinonitrile (A-740)

[0290] [ka]

[0291] Under an argon atmosphere, 2-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2-yl)-4,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (3.5 g, 4.8 mmol), 5-bromopicolinonitrile (2.1 g, 11 mmol), and tetrakis(triphenylphosphine)palladium (0) (0.28 g, 0.24 mmol) were suspended in THF (45 mL). 2M potassium carbonate aqueous solution (14 mL, 29 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 pyridine heated to 115°C, activated carbon was added and the mixture was stirred, then filtered hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered off to obtain 5,5'-((6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))dipicolinonitrile (A-740) (yield 2.0 g, yield 61%).

[0292] 1 H-NMR(400MHz,CDCl3)δ(ppm):9.07(dd,J=2.3,0.8Hz,2H),8.92(brd,J=8.5Hz,4H),8.79(brd,J=1.5Hz,1H),8.51(dd,J=7.8,1.5Hz,1H),8.13(dd,J=8.0 ,2.3Hz,2H),7.84(dd,J=8.0,0.8Hz,2H),7.83(brd,J=8.5Hz,4H),7.61(d,J =7.8Hz,1H),7.51-7.43(m,4H),7.08-7.02(m,4H),5.67(s,1H),5.57(s,1H).

[0293] <Synthesis Example-10> 4',4'''-(6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis([1,1'-biphenyl]-4-carbonitrile)(A-327)

[0294] [ka]

[0295] Under an argon atmosphere, 2,4-bis(4-chlorophenyl)-6-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2-yl)-1,3,5-triazine (2.5 g, 4.5 mmol), 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile (2.3 g, 11 mmol), palladium acetate (51 mg, 0.23 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.22 g, 0.45 mmol) were suspended in THF (45 mL). 2M potassium carbonate aqueous solution (16 mL, 33 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 obtained solid was dissolved in toluene heated to 110°C and filtered while hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered to obtain 4',4'''-(6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine-2,4-diyl)bis([1,1'-biphenyl]-4-carbonitrile)(A-327) (yield 2.8g, yield 90%).

[0296] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.87(brd,J=8.6Hz,4H),8.78(d,J=1.6Hz,1H),8.50(dd,J=7.7,1.6Hz,1H), 7.84-7.76(m,12H),7.61(d,J=7.7Hz,1H),7.51-7.42(m,4H),7.07-7.01(m,4H),5.67(s,1H),5.57(s,1H).

[0297] <Synthesis Example-11> 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2-yl)phenyl)-6-phenyl-1,3,5-triazine-2-yl)isophthalonitrile (A-956)

[0298] [ka]

[0299] Under an argon atmosphere, 5-(4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine-2-yl)isophthalonitrile (1.7 g, 4.3 mmol), 2-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.8 g, 4.8 mmol), palladium acetate (29 mg, 0.13 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.12 g, 0.26 mmol) were suspended in THF (43 mL). 2M potassium carbonate aqueous solution (7.2 mL, 14 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 obtained solid was dissolved in toluene heated to 110°C and filtered while hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered to obtain 5-(4-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)phenyl)-6-phenyl-1,3,5-triazine-2-yl)isophthalonitrile (A-956) (yield 1.5g, yield 56%).

[0300] 1H-NMR(400MHz,CDCl3)δ(ppm):9.26(d,J=1.2Hz,2H),8.79-8.74(m,4H),8.12(brt,J=1.2Hz,1H),7.77-7.72(m,3H),7.69(brt,J=7.2Hz,1H ),7.65-7.70(m,2H),7.52(brd,J=7.6Hz,1H),7.48-7.41(m,4H),7.35(dd,J=7.6,1.7Hz,1H),7.06-7.01(m,4H),5.56(s,1H),5.51(s,1H).

[0301] <Synthesis Example-12> 4',4'''-{6-[4-(1-adamantyl)phenyl]-1,3,5-triazine-2,4-diyl}bis[(1,1'-biphenyl)-4-carbonitrile](A-325) [ka]

[0302] Under a nitrogen atmosphere, 2-[4-(1-adamantyl)phenyl]-4,6-bis(4-chlorophenyl)-1,3,5-triazine (0.63 g, 1.2 mmol), 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile (0.56 g, 2.6 mmol), palladium acetate (8.5 mg, 0.038 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (35.4 mg, 0.074 mmol) were suspended in THF (12 mL). 2M tripotassium phosphate aqueous solution (3.7 mL, 7.4 mmol) was added to this suspension, and the mixture was refluxed for 3.5 hours. After filtering the reaction solution, the resulting solid was washed with water, methanol, and hexane, and then vacuum-dried and recrystallized with toluene to obtain 4',4'''-{6-[4-(1-adamantyl)phenyl]-1,3,5-triazine-2,4-diyl}bis[(1,1'-biphenyl)-4-carbonitrile](A-325) (yield 0.51g, yield 64%).

[0303] 1H-NMR(400MHz,CDCl3)δ(ppm):8.89(d,J=8.7Hz,4H),8.73(d,J=8.6Hz,2H), 7.78-7.83(m,12H),7.60(d,J=8.6Hz,2H),2.16(brs,3H),2.01(d,J=2.7Hz,6H),1.83(brt,J=15.2Hz,6H).

[0304] <Synthesis Example-13> 4-(3-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2-yl)-6-phenyl-1,3,5-triazine-2-yl)phenyl)pyridine-2,6-dicarbonitride (A-609)

[0305] [ka]

[0306] Under a nitrogen atmosphere, 2-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2-yl)-4-phenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (1.5 g, 2.5 mmol), 4-chloropyridine-2,6-dicarbonitride (0.53 g, 3.3 mmol), palladium acetate (12 mg, 0.053 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (50 mg, 0.11 mmol) were suspended in THF (25 mL). 2M tripotassium phosphate aqueous solution (3.7 mL, 7.4 mmol) was added to this suspension, and the mixture was refluxed for 5 hours. The reaction solution was allowed to cool to room temperature, ethanol was added, and the solid was filtered and washed with water, methanol, and hexane. The obtained solid was dissolved in a mixed solvent of 25 mL of toluene and 25 mL of pyridine and heated to 110°C. 0.17 g of activated carbon was added to this solution, and it was filtered while hot using Celite. The filtrate was allowed to stand at room temperature, and the precipitated solid was filtered to obtain 4-(3-(4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-6-phenyl-1,3,5-triazine-2-yl)phenyl)pyridine-2,6-dicarbonitrile (A-609) (yield 1.3 g, yield 87%).

[0307] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.97-8.94(m,2H),8.75(m,1H),8.73(t,J=1.8Hz,2H),8.46(dd,J=7.8,1.7Hz,1H), 8.19(s,2H),7.82-7.76(m,2H),7.67-7.58(m,4H),7.49-7.44(m,4H),7.07-7.02(m,4H),5.66(s,1H),5.57(s,1H).

[0308] <Synthesis Example-14> 2-{5'-[4-(adamantan-1-yl)phenyl]-1,1':2',1''-terphenyl-3-yl}-4,6-diphenyl-1,3,5-triazine (A-966)

[0309] [ka]

[0310] Following the same procedure as in Synthesis Example-1, the target product, 2-{5'-[4-(adamantan-1-yl)phenyl]-1,1':2',1''-terphenyl-3-yl}-4,6-diphenyl-1,3,5-triazine (compound A-966), was obtained as a white solid (84% yield).

[0311] 1 H-NMR(CDCl3)δ(ppm):1.79(s,6H),1.98(d,J=2.8Hz,6H),2.13(s,3H),7.17(t,J=7.2Hz,1H),7.22-7.30(m,4H),7.38-7.45(m,2H),7.4 8(d,J=8.6Hz,2H),7.55-7.64(m,7H),7.67-7.74(m,3H),7.80(d,J=1.8Hz,1H),8.65(d,J=7.1Hz,1H),8.68(s,1H),8.73(d,J=6.5Hz,4H)

[0312] <Synthesis Example-15> 4-(adamantan-1-yl)-6-(4'-(6-(adamantan-1-yl)-2-phenylpyrimidine-4-yl)-[1,1'-biphenyl]-4-yl)-2-phenylpyrimidine (A-969)

[0313] [ka]

[0314] A white solid (yield 28%) of the target product, 4-(adamantan-1-yl)-6-(4'-(6-(adamantan-1-yl)-2-phenylpyrimidine-4-yl)-[1,1'-biphenyl]-4-yl)-2-phenylpyrimidine (A-969), was obtained using the same procedure as in Synthesis Example-1.

[0315] 1H-NMR(CDCl3)δ(ppm):8.69-8.67(m,4H),8.35(d,J=8.4Hz,4H),7.84(d,J=8.6H z,4H),7.60(s,2H),7.55-7.47(m,6H),2.20-2.15(m,18H),1.89-1.83(m,12H).

[0316] <Synthesis Example-16> [ka]

[0317] Under an argon atmosphere, 2-bromo-6-chloro-1,1'-biphenyl (3.6 g, 14 mmol) was suspended in tetrahydrofuran (62 mL), and 1.6 Mn-butyllithium solution (10 mL, 16 mmol) was added dropwise, and the mixture was stirred at -78°C for 1 hour. A solution of 3-diamantanone (2.5 g, 12 mmol) dissolved in tetrahydrofuran (62 mL) was added dropwise, and the mixture was stirred at room temperature for 10 hours. The resulting organic layer was concentrated and suspended in trifluoroacetic acid (4.2 mL) and 1,2-dichlorobenzene (55 mL), and stirred at 120°C for 3 hours. After cooling to 0°C, aqueous potassium carbonate solution and toluene were added, and the organic layer was extracted by liquid-liquid extraction. The resulting organic layer was concentrated and purified by column chromatography to obtain the target 4-chloro-spiro(9H-fluorene-9,3'-diamantane) (yield 3.2 g, yield 79%).

[0318] 1 H-NMR(CDCl3)δ(ppm):8.73(dd,J=1.2Hz,7.6Hz,1H),8.16(d,J=8.0Hz,1H),8.08(d,J=7.6Hz,1H),7.29-7.43(m,3H) ),7.17(t,J=8.0Hz,8.0Hz,1H),2.88-3.06(m,3H),2.11(s,2H),1.77-1.89(m,6H),1.57-1.73(m,6H),1.39(s,1H).

[0319] 2-(3'-((4'R,4a'S,8'R,11'S)-3',4',4a',5',6',7',8',8a'-Octahydro-2'H-Spiro[Fluorene-9,1'-[2,8,4,6](Epibutane[1,2,3,4]tetrayl)naphthalene]-4-yl)-[1,1'-Biphenyl]-3-yl)-4,6-Diphenyl-1,3,5-Triadine (A-978)

[0320] [ka]

[0321] Under an argon atmosphere, 2,4-diphenyl-6-[3'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)[1,1'-biphenyl]-3-yl]-1,3,5-triazine (1.4 g, 2.7 mmol), 4-chlorospiro(9H-fluoren-9,3'-diamantane) (1.1 g, 3.0 mmol), palladium acetate (18 mg, 0.080 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.66 g, 0.16 mmol) were dissolved in THF (27 mL). A 2 M potassium phosphate aqueous solution (4.0 mL, 8.0 mmol) was added, and the mixture was stirred at 70°C for 4 hours. After cooling to room temperature, the precipitate was removed by filtration. After cooling to room temperature, methanol was added, and the precipitated solid was filtered off. The filtered material was suspended in toluene (300 mL), heated to 100°C, and then activated carbon was added and stirred before being filtered by Celite. The filtrate was concentrated and purified by recrystallization with toluene to obtain a white solid of compound (A-978) (1.0 g, yield 52%).

[0322] 1H-NMR(CDCl3)δ(ppm):9.04(s,1H),8.75-8.78(m,5H),8.22(d,J=8.8Hz,1H),8.15(d,J=8.0Hz,1H),7.81-7.88(m,3H),7.48-7.68(m, 10H),7.32(dd,J=8.0Hz,15.6Hz,2H),7.14-7.18(m,1H),7.05(d,J=4.4Hz,2H),2.98-3.12(m,4H),2.14(brs,2H),1.56-1.91(m,11H).

[0323] <Synthesis Example-17> 2-(4-(4-(4-(adamantan-1-yl)phenyl)-6-phenyl-1,3,5-triazine-2-yl)phenyl)dibenzothiophen-5,5-dioxide (D-60)

[0324] [ka]

[0325] Under a nitrogen atmosphere, 2-(4-(adamantan-1-yl)phenyl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (0.65 g, 1.4 mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzothiophene-5,5-dioxide (0.49 g, 1.4 mmol), palladium acetate (7.1 mg, 0.032 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (21.8 mg, 0.046 mmol) were suspended in THF (14 mL). 2.0 mL, 4.1 mmol of 2 M tripotassium phosphate aqueous solution was added to this suspension, and the mixture was refluxed for 8 hours. The reaction solution was allowed to cool to room temperature, 45 mL of ethanol and 5 mL of water were added, and the mixture was stirred at room temperature before the solid was filtered off. The obtained solid was washed with water, ethanol, and THF to obtain 2-(4-(4-(4-(adamantan-1-yl)phenyl)-6-phenyl-1,3,5-triazine-2-yl)phenyl)dibenzothiophen-5,5-dioxide (D-60) (yield 0.71g, yield 80%).

[0326] 1 H-NMR(400MHz,CDCl3)δ(ppm):8.91(d,J=8.3Hz,2H),8.81-8.79(m,2H),8.73(d,J=8.6Hz,2H),8.07(s,1H),7.95(t,J=8.3Hz,2H),7.88(d,J=7. 5Hz,1H),7.84(d,J=8.4Hz,3H),7.71(td,J=7.6,1.2Hz,1H),7.64-7.57(m,6H),2.16(brs,3H),2.01(d,J=2.9Hz,6H),1.82(brt,J=14.3Hz,6H).

[0327] <Synthesis Example-18> 2,5-Bis(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)-2,5-diazabicyclo[2.2.1]heptane(A-981)

[0328] [ka]

[0329] Under a nitrogen atmosphere, (1S,4S)-2,5-diazabicyclo[2.2.1]heptane hydrobromide (0.30 g, 1.2 mmol), potassium hydroxide (0.33 g, 5.9 mmol), 12 mL of THF, and 1 mL of water were added and stirred at room temperature for 2.5 hours. To this suspension, a solution of 2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (1.0 g, 2.1 mmol) dissolved in 20 mL of THF was added dropwise and stirred at room temperature for 2.5 hours. The precipitated solid was filtered off, and the resulting solid was washed with water, acetone, and THF to obtain 2,5-bis(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-2,5-diazabicyclo[2.2.1]heptane (A-981) (yield 0.70 g, yield 70%).

[0330] 1H-NMR(400MHz,CDCl3)δ(ppm):8.72(d,J=8.6Hz,4H),8.64(d,J=8.6Hz,4H),7.78(d,J=8.6Hz,4H),7.71(t,J =8.7Hz,8H),7.66-7.63(m,4H),7.53-7.35(m,12H),5.58(s,2H),4.04(q,J=16.4,10.7Hz,4H),2.28(s,2H).

[0331] <Glass transition temperature> The glass transition temperatures of compounds A-960, A-396, A-952, A-918, A-942, A-944, A-949, A-955, A-740, A-327, A-956, A-325, A-609, A-966, A-969, A-978, A-981, and D-60 from Synthesis Examples 1 to 18, as well as comparative compound 1 described in Reference 2, were measured using a differential scanning calorimeter (Hitachi High-Tech DSC7020) with an aluminum pan at a sweep rate of 10°C / min. The obtained glass transition temperature results are summarized in the table below.

[0332] [ka]

[0333] [Table 1-1]

[0334] [Table 1-2]

[0335] [Table 1-3]

[0336] The results shown in the table above indicate that the material for the photoelectric conversion element for the image sensor used to form the layer of the image sensor according to one embodiment of the present invention has superior thermal stability of the film compared to comparative compound 1.

[0337] <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.

[0338] (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.

[0339] (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.

[0340] 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.

[0341] (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-942) at a rate of 0.03 nm / second.

[0342] (Fabrication of photoelectric conversion layer (light-receiving layer) 3) A photoelectric conversion layer 3 was fabricated by co-evaporating 2Ph-BTBT, F6-SubPc-OC6F5, and fullerene (C60) at a deposition rate ratio of 4:4:2 to a thickness of 200 nm. The deposition rate was 0.15 nm / second.

[0343] (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.

[0344] (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.

[0345] (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, gold 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.

[0346] As a result, the area shown in Figure 1 is 4 mm². 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).

[0347] 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).

[0348] 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.

[0349] 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.

[0350] <Examples of Element Types 2-10, Comparative Example of Element Type 1> In Element Example-1, an imaging photoelectric conversion element was fabricated and evaluated using the same method as in Element Example-1, except that compounds A-949, A-327, A-956, A-609, A-952, A-918, A-960, A-396, and A-944, respectively, and comparative compound 1 described in Reference 1, were used instead of compound (A-942). The obtained measurement results are shown in the table below.

[0351] [Table 2]

[0352] The results in the table above show that by forming a layer using the material for the photoelectric conversion element for image sensors used to form the layer in an image sensor according to one aspect of the present invention, an image sensor photoelectric conversion element with superior responsiveness, high external quantum efficiency, and reduced dark current can be realized compared to the case where a layer is formed using comparative example compounds. [Industrial applicability]

[0353] 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]

[0354] 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 (1) for the photoelectric conversion element for the image sensor is It has at least one tetrahedron-shaped solid part (2), The aforementioned tetrahedral-shaped three-dimensional portion (2) has a central atom (3) at the center of the tetrahedron, At the vertices of the tetrahedron, there are sites selected from the lone pair of electrons (4) of the central atom (3) and three or four adjacent atoms (5) bonded to the central atom (3). Furthermore, it has a first annular structure and a second annular structure which is condensed with the first annular structure, The first cyclic structure includes the central atom (3) and two of the adjacent atoms (5), The first cyclic structure or the second cyclic structure has at least one substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heteroaromatic group. The aforementioned aromatic hydrocarbon group or heteroaromatic group is a monoring, a linking ring containing multiple rings, or a fused ring. An image sensor in which the molecular weight of the material (1) for the photoelectric conversion element of the image sensor is 500 or more.

2. The material (1) for the photoelectric conversion element for the image sensor has at least one of the three-dimensional structures represented by the following formulas (2-1) to (2-9), including the three-dimensional portion (2), the first annular structure, and the second annular structure; 【Chemistry 1】 In the above formulas (2-1) to (2-9), W １ and W ２ Each of these independently represents either C-Ra or N; W ３ Each of these independently is C(-Ra) ２ , or representing N-Ra; Ra represents, either identical or distinct, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted hydrocarbon group, a hydrogen atom, a halogen atom, or a cyano group; * indicates a bonding site with an adjacent group; The stereostructures of formulas (2-1) to (2-9) may be unsubstituted or have substituents; The three-dimensional structures of the above formulas (2-1) to (2-9) may be further connected to or fused with three-dimensional parts (2). The image sensor according to claim 1, wherein at least one of the Ra is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heteroaromatic group, and the aromatic hydrocarbon group or heteroaromatic group is a monoring, a linking ring containing multiple rings, or a fused ring.

3. The image sensor according to claim 2, wherein the glass transition temperature of the material (1) for the photoelectric conversion element for the image sensor is 140°C or higher.

4. The image sensor according to claim 2, wherein the central atom (3) of the material (1) for the photoelectric conversion element for the image sensor is a carbon atom, a nitrogen atom, a silicon atom, a phosphorus atom, or a sulfur atom.

5. The image sensor according to claim 2, wherein the first annular structure in the material (1) for the photoelectric conversion element for the image sensor, including the central atom (3) of the three-dimensional portion (2), is a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or an eight-membered ring.

6. The image sensor according to claim 2, wherein the second annular structure in the material (1) for the photoelectric conversion element for the image sensor is a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or an eight-membered ring.

7. The glass transition temperature of the material (1) for the image sensor photoelectric conversion element is 140°C or higher; In the aforementioned photoelectric conversion element material (1) for the image sensor, the central atom (3) is a carbon atom, a nitrogen atom, a silicon atom, a phosphorus atom, or a sulfur atom; The first annular structure in the material (1) for the photoelectric conversion element for the image sensor is a five-membered ring or a six-membered ring; The image sensor according to claim 2, wherein the second annular structure in the material (1) for the photoelectric conversion element for the image sensor is a five-membered ring or a six-membered ring.

8. The image sensor according to any one of claims 1 to 7, wherein the material (1) for the photoelectric conversion element for the image sensor has at least one electron acceptor portion.

9. Compounds represented by the following formula (6) having a tetrahedral stereochemical region (2): 【Chemistry 2】 In the above formula (6), Ar １ ~Ar ３ Each of these independently represents 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 １ ~L ３ Each of these independently represents a 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; The number of carbon atoms in the aforementioned aromatic hydrocarbon group is 6 to 28; The number of carbon atoms in the heteroaromatic group is 3 to 24; The number of carbon atoms in the cyclic aliphatic hydrocarbon group is 10 to 16; a １ 、a ２ 、b １ 、b ２ 、c １ 、and c ２ each independently represents an integer of 1 to 3; p, q, and r each independently represent integers between 0 and 3; Ar １ Ar ２ , and Ar ３ At least one of them has a three-dimensional structure including the three-dimensional portion (2) represented by formula (2-8-1); 【Transformation 3】 In the above formula (2-8-1), * indicates a bonding site with an adjacent group; Ar １ Ar ２ Ar ３ , L １ , L ２ , and L ３ In these groups, the sum of the number of cyano groups, the number of adamantyl groups, and the number of groups represented by formula (2-8-1) is 2 or more; The molecular weight of the compound represented by formula (6) is 550 or more.

10. The Ar １ Ar ２ Ar ３ , L １ , L ２ , and L ３ At least one of these is the compound according to claim 9, represented by formula (2-8-1).

11. a １ a ２ , b １ , b ２ , c １ , and c ２ The compound according to claim 9, wherein each of them is independently an integer of 1 or 2.

12. The compound according to claim 9, wherein p, q, and r are each independently integers from 0 to 2.

13. Ar １ ~Ar ３ The compound according to claim 9, wherein each of the groups is independently a substituted or unsubstituted divalent to trivalent phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, triphenylenyl group, dibenzocrisenyl group, triazyl group, pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuryl group, benzothienyl group, dibenzofuryl group, or dibenzothienyl group.

14. L １ ~L ３ The compound according to claim 9, wherein each of the groups is independently a substituted or unsubstituted divalent to tetravalent phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, triphenylenyl group, dibenzocrisenyl group, triazyl group, pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuryl group, benzothienyl group, dibenzofuryl group, or dibenzothienyl group.

15. A material for a photoelectric conversion element for an image sensor, comprising the compound described in any one of claims 9 to 14.

16. A hole-blocking material, which is a material for a photoelectric conversion element for an image sensor according to claim 15.

17. An image sensor comprising a layer containing the material for a photoelectric conversion element for an image sensor as described in claim 16.

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