Photoelectric conversion element, imaging element, optical sensor, and compound

Abstract

The present invention addresses the problem of providing a photoelectric conversion element that has excellent quantum efficiency and excellent suitability for manufacturing. The present invention also addresses the problem of providing an imaging element, an optical sensor, and a compound which relate to the photoelectric conversion element. A photoelectric conversion element according to the present invention comprises a conductive film, a photoelectric conversion film, and a transparent conductive film in this order. The photoelectric conversion film includes a compound represented by formula (1).

Description

Photoelectric conversion elements, imaging elements, optical sensors, compounds

[0001] The present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, and a compound.

[0002] In recent years, development of devices (e.g., image sensors) having photoelectric conversion films has progressed. For example, Patent Document 1 discloses a compound having a specific structure as a material used in photoactive organic electronic components.

[0003] Special table 2019-508376 publication

[0004] With the demand for improved performance of imaging devices, optical sensors, and the like, there is a demand for photoelectric conversion devices that exhibit excellent characteristics. Examples of the characteristics required for photoelectric conversion devices include quantum efficiency. Furthermore, from the viewpoint of device manufacturing efficiency, photoelectric conversion devices are also required to exhibit excellent manufacturability, such that the characteristics of the photoelectric conversion device do not deteriorate even when the deposition rate is increased. In response to such demands, the present inventors fabricated and investigated a photoelectric conversion device containing the compound disclosed in Patent Document 1, and found that it was difficult to achieve both quantum efficiency and manufacturability.

[0005] Therefore, an object of the present invention is to provide a photoelectric conversion element that is excellent in quantum efficiency and manufacturability, and also to provide an imaging element, an optical sensor, and a compound related to the photoelectric conversion element.

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described below. [2] X １ [3] The photoelectric conversion element according to [1], wherein X is an oxygen atom. １ and X ３is an oxygen atom. [4] The photoelectric conversion element according to any one of [1] to [3], wherein the group represented by formula (A-1) described later is a group represented by formula (A-2) described later. [5] The photoelectric conversion element according to any one of [1] to [4], wherein the group represented by formula (A-1) described later is a group represented by formula (C-1) described later or a group represented by formula (C-2) described later. [6] R Ｚ２ is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from Substituent Group S, an acyl group having 2 to 5 carbon atoms, an aromatic ring group which may have a substituent selected from Substituent Group S, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group S, or -Si(R Ｓｉ２ ) ３ The photoelectric conversion element according to any one of [1] to [5], wherein R represents a group represented by Ｚ２ The linear aliphatic hydrocarbon having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above substituent group S may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group having 2 to 5 carbon atoms, represented by the following formula (I), may have a halogen atom. Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a halogen atom, and —Si(R Ｓｉ２ ) ３ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the above substituent group S may contain a halogen atom or an etheric oxygen atom. Ｓｉ２R each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group S. Ｓｉ２ The linear aliphatic hydrocarbon having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S may have a halogen atom or an etheric oxygen atom. [7] R Ｚ２ is a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, an acyl group having 2 or 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, an aromatic ring group which may have a substituent selected from Substituent Group T, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group T, or -Si(R Ｓｉ３ ) ３ The photoelectric conversion element according to any one of [1] to [6], wherein the substituent group T is a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, a halogen atom, and —Si(R Ｓｉ３ ) ３ A group represented by R Ｓｉ３each independently represent a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned Substituent Group T, or an aromatic ring group which may have a substituent selected from the above-mentioned Substituent Group T. [8] The photoelectric conversion element according to any one of [1] to [7], wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed by mixing a compound represented by Formula (1) described below with the n-type organic semiconductor. [9] The photoelectric conversion element according to [8], wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof.

[10] The photoelectric conversion element according to any one of [1] to [9], wherein the photoelectric conversion film further contains a p-type organic semiconductor.

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

[10] , wherein the photoelectric conversion film further contains a dye.

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

[11] , which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

[13] An imaging element having the photoelectric conversion element according to any one of [1] to

[12] .

[14] An optical sensor having the photoelectric conversion element according to any one of [1] to

[12] .

[15] A compound represented by formula (1) described later.

[16] X １

[17] The compound according to

[15] , wherein X is an oxygen atom. １ and X ３ is an oxygen atom.

[18] The compound according to any one of

[15] to

[17] , wherein the group represented by formula (A-1) described later is a group represented by formula (A-2) described later.

[19] The compound according to any one of

[15] to

[18] , wherein the group represented by formula (A-1) described later is a group represented by formula (C-1) described later or a group represented by formula (C-2) described later.

[20] R Ｚ２is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from Substituent Group S, an acyl group having 2 to 5 carbon atoms, an aromatic ring group which may have a substituent selected from Substituent Group S, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group S, or -Si(R Ｓｉ２ ) ３ The compound according to any one of

[15] to

[19] , wherein R represents a group represented by Ｚ２ The linear aliphatic hydrocarbon having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above substituent group S may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group having 2 to 5 carbon atoms, represented by the following formula (I), may have a halogen atom. Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a halogen atom, and —Si(R Ｓｉ２ ) ３ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the above substituent group S may contain a halogen atom or an etheric oxygen atom. Ｓｉ２ R each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group S. Ｓｉ２ The linear aliphatic hydrocarbon having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S may have a halogen atom or an etheric oxygen atom.

[21] R Ｚ２is a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, an acyl group having 2 or 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, an aromatic ring group which may have a substituent selected from Substituent Group T, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group T, or -Si(R Ｓｉ３ ) ３ The compound according to any one of

[15] to

[20] , wherein the substituent group T is a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, a halogen atom, and —Si(R Ｓｉ３ ) ３ A group represented by R Ｓｉ３ each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned substituent group T, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group T.

[0008] According to the present invention, a photoelectric conversion element having excellent quantum efficiency and excellent manufacturability can be provided. Furthermore, according to the present invention, an imaging element, an optical sensor, and a compound related to the photoelectric conversion element can also be provided.

[0009] 1 is a schematic cross-sectional view showing an example of the configuration of a photoelectric conversion element.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] In this specification, a hydrogen atom may be either a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom). In this specification, when there are multiple substituents, linking groups, etc. (hereinafter also referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are specified at the same time, this means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.

[0013] In this specification, unless otherwise specified, examples of the "substituent" include the groups exemplified as the substituent W below.

[0014] (Substituent W) The substituent W in this specification will be described. Examples of the substituent W include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a secondary or tricyclic group, a cycloalkenyl ... Examples of the substituent W include primary amino groups (including anilino groups), alkylthio groups, arylthio groups, heterocyclic thio groups, alkyl or arylsulfinyl groups, alkyl or arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, aryl or heterocyclic azo groups, imido groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, carboxy groups, phosphate groups, sulfonic acid groups, hydroxy groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, boronic acid groups, and primary amino groups. Furthermore, each of the above groups may further have a substituent (e.g., one or more of the above groups, etc.) if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. Furthermore, when the substituent W has carbon atoms, the number of carbon atoms contained in the substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30. The specific compounds described below may have, as substituents, a carboxy group, a salt of a carboxy group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) ２ ) and / or does not have a primary amino group.

[0015] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0016] In this specification, the aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. In addition, unless otherwise specified in this specification, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, and a cyclopentyl group. In addition, the alkyl group may be a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have these ring structures as partial structures. In the alkyl group that may have a substituent, examples of the substituent that the alkyl group may have include the groups exemplified for the substituent W. Of these, an aryl group (preferably having 6 to 18 carbon atoms, more preferably having 6 carbon atoms), a heteroaryl group (preferably having 5 to 18 carbon atoms, more preferably having 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom) is preferred.

[0017] In this specification, unless otherwise specified, the alkyl group moiety in the alkoxy group is preferably the above-mentioned alkyl group. The alkyl group moiety in the alkylthio group is preferably the above-mentioned alkyl group. In the alkoxy group which may have a substituent, examples of the substituent that the alkoxy group may have include the same as the substituent in the alkyl group which may have a substituent. In the alkylthio group which may have a substituent, examples of the substituent that the alkylthio group may have include the same as the substituent in the alkyl group which may have a substituent.

[0018] In this specification, unless otherwise specified, the alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20. In the alkenyl group which may have a substituent, examples of the substituent that the alkenyl group may have include the same as the substituents in the alkyl group which may have a substituent. In this specification, unless otherwise specified, the alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20. In the alkynyl group which may have a substituent, examples of the substituent that the alkynyl group may have include the same as the substituents in the alkyl group which may have a substituent.

[0019] In this specification, unless otherwise specified, an aromatic ring or an aromatic ring constituting an aromatic ring group may be either a monocyclic ring or a polycyclic ring (e.g., 2 to 6 rings). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure. A polycyclic (e.g., 2 to 6 rings) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6) condensed aromatic ring structures as a ring structure. The number of ring members in the aromatic ring is preferably 5 to 15. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. When the aromatic ring is an aromatic heterocyclic ring, the number of heteroatoms contained as ring member atoms is, for example, 1 to 10. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring.Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (e.g., a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (e.g., a 1,2,4,5-tetrazine ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a naphthopyrrole ring, a naphthofuran ring, a naphthothiophene ring, a naphthoimidazole ring, a naphthoxazole ring, a pyrroloimidazole ring (e.g., a 5H-pyrrolo[1,2-a]imidazole ring), an imidazooxazole ring (e.g., an imidazo[2,1-b]oxazole ring). , thienothiazole rings (for example, thieno[2,3-d]thiazole rings, etc.), benzothiadiazole rings, benzodithiophene rings (for example, benzo[1,2-b:4,5-b']dithiophene rings, etc.), thienothiophene rings (for example, thieno[3,2-b]thiophene rings, etc.), thiazolothiazole rings (for example, thiazolo[5,4-d]thiazole rings, etc.), naphthodithiophene rings (for example, naphtho[2,3 [2,1-b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc.), benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring, and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring.

[0020] In the aromatic ring which may have a substituent, the type of the substituent which the aromatic ring may have can be, for example, the groups exemplified as the substituent W. When the aromatic ring has a substituent, the number of the substituents may be 1 or more (for example, 1 to 4).

[0021] As used herein, the term "aromatic ring group" includes, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic ring. As used herein, the term "aryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic hydrocarbon ring among the above-mentioned aromatic rings. As used herein, the term "heteroaryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic heterocyclic ring among the above-mentioned aromatic rings. As used herein, the term "arylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above-mentioned aromatic rings. As used herein, the term "heteroarylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocyclic ring among the above-mentioned aromatic rings. In the optionally substituted aromatic ring group, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted arylene group, and optionally substituted heteroarylene group, the types of substituents that these groups may have include, for example, the groups exemplified for the substituent W. When these groups which may have a substituent have a substituent, the number of the substituents may be one or more (for example, 1 to 4, etc.).

[0022] As used herein, the term "non-aromatic ring" refers to a ring that does not qualify as aromatic, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle. Examples of the aliphatic hydrocarbon ring include a cycloalkane, a cycloalkene, and a cycloalkyne. Examples of the aliphatic heterocycle include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, and a γ-butyrolactone ring. As used herein, the term "aliphatic hydrocarbon ring group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that corresponds to an aliphatic hydrocarbon ring. As used herein, the term "aliphatic heterocyclic group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that corresponds to an aliphatic heterocycle.

[0023] In this specification, when a formula showing a chemical structure contains a plurality of identical symbols indicating the type or number of groups, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different, unless otherwise specified. In this specification, when a formula showing a chemical structure contains a plurality of groups of the same type (e.g., alkyl groups, etc.), the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the plurality of groups of the same type may be the same or different, unless otherwise specified.

[0024] In this specification, the bonding direction of a divalent group (e.g., -CO-O-, etc.) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be either "X-O-CO-Z" or "X-CO-O-Z."

[0025] In this specification, with respect to compounds that may have geometric isomers (cis-trans isomers), the general formula or structural formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.

[0026] In this specification, unless otherwise specified, * in a formula indicates a bonding position.

[0027] [Photoelectric conversion element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a photoelectric conversion film and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) described later (hereinafter also referred to as a "specific compound").

[0028] Although the reason why the treatment solution having the above-mentioned constitution can solve the problem of the present invention is not entirely clear, the present inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the following, it is included in the scope of the present invention. The specific compound has a structure in which RＺ２ and X １ ~X ３ When at least one of the groups is an oxygen atom, the intermolecular interaction of the specific compound is appropriately controlled. This suppresses excessive aggregation between the specific compounds, and charge separation in the photoelectric conversion film proceeds efficiently, resulting in excellent quantum efficiency of the photoelectric conversion element. Furthermore, when the acceptor moiety of the specific compound has a specific ring structure and the donor moiety has R Ｚ２ and X １ ~X ３ When at least one of the atoms is an oxygen atom, the heat resistance and sublimation temperature of the specific compound are appropriately controlled. This suppresses decomposition of the specific compound even when the deposition rate is increased, resulting in excellent manufacturability. Hereinafter, when at least one of the quantum efficiency and manufacturability of the photoelectric conversion element is excellent, it is also referred to as "excellent effects of the present invention."

[0029] FIG. 1 shows a cross-sectional schematic diagram of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in FIG. 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 functioning as an upper electrode are stacked in this order. FIG. 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in FIG. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be changed as appropriate depending on the application and characteristics.

[0030] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15. When the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 is applied between the pair of electrodes. －５ ~1 x 10 ７In terms of performance and power consumption, it is preferable to apply a voltage of 1×10 V / cm. －４ ~1 x 10 ７ V / cm is more preferable, and 1×10 －３ ~5 x 10 ６ V / cm is more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an imaging element, a voltage can be applied in a similar manner. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0031] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film.

[0032] <Specific Compound> The photoelectric conversion film contains a specific compound, which is a compound represented by formula (1).

[0033]

[0034] In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. １ ~X ３ each independently represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom. １ ~X ３ At least one of Z is an oxygen atom. １ ~Z ６ are each independently -CR Ｚ１ = or -N=. Ｚ１ represents a hydrogen atom or a substituent. １ ~Z ６ At least one of the groups is -CR Ｚ２ = R Ｚ２ represents an aliphatic hydrocarbon group which may have a substituent, an acyl group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or —Si(R Ｓｉ) ３ R represents a group represented by the formula: Ｚ２ The aliphatic hydrocarbon group represented by the formula (I) may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group represented by the formula (I) may have a halogen atom. Ｓｉ R each independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. Ｓｉ The aliphatic hydrocarbon group represented by the following formula may have a halogen atom or an etheric oxygen atom. １ and Z ２ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ３ and Z ４ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ５ and Z ６ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring. １ and A ２ each independently represents a group represented by formula (A-1). １ represents a ring containing at least two carbon atoms, which may have a substituent. １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ represents a hydrogen atom or a substituent. Ｗ２ and R Ｗ３ each independently represents a cyano group, —SO ２ R Ｗ４ , -COOR Ｗ５ or -COR Ｗ６ Represents R Ｗ４ , R Ｗ５ and R Ｗ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

[0035] In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W. In terms of the effects of the present invention being more excellent, R １ and R ２ is preferably a hydrogen atom.

[0036] In formula (1), X １ ~X ３ each independently represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom. １ ~X ３ At least one of X is an oxygen atom. １ ~X ３ is preferably a sulfur atom or an oxygen atom, more preferably an oxygen atom. １ ~X ３ Among these, at least one is an oxygen atom, and preferably two or more are oxygen atoms. １ and X ３ Preferably, at least one of X is an oxygen atom, １ and X ３ is more preferably an oxygen atom.

[0037] The compound represented by formula (1) is preferably a compound represented by formula (1-1) to formula (1-5), more preferably a compound represented by formula (1-1) to formula (1-4), still more preferably a compound represented by formula (1-1) or a compound represented by formula (1-4), and particularly preferably a compound represented by formula (1-1).

[0038]

[0039] In formulas (1-1) to (1-5), R １ , R ２ , Z １ ~Z ６ , A １ and A ２ is R in formula (1) １ , R ２ , Z１ ~Z ６ , A １ and A ２ It is synonymous with X. ４ and X ５ each independently represents a sulfur atom, a selenium atom, or a tellurium atom. ４ and X ５ is preferably a sulfur atom.

[0040] In formula (1), Z １ ~Z ６ are each independently -CR Ｚ１ = or -N=. Ｚ１ represents a hydrogen atom or a substituent. Ｚ１ Examples of the substituent represented by the formula (I) include the substituents exemplified as the substituent W described above. Ｚ１ is a hydrogen atom, a halogen atom, or R Ｚ２ It is preferable that R Ｚ１ If there are multiple R Ｚ１ The groups represented by may be the same or different. １ ~Z ６ At least one of them is -CR Ｚ１ = and at least three are -CR Ｚ１ =, and at least five are -CR Ｚ１ It is more preferable that .gtoreq..times ...

[0041] In formula (1), Z １ ~Z ６ At least one of them is -CR Ｚ２ = Z １ ~Z ６ 1 to 4 of them are -CR Ｚ２ It is preferable that R Ｚ２ If there are multiple R Ｚ２ The groups represented by may be the same or different. １ and Z ２ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ３ and Z ４ Ga-CRＺ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ５ and Z ６ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring. Ｚ２ Examples of the ring formed by bonding together include an aliphatic hydrocarbon ring and an aliphatic heterocycle. The number of members in the ring is not particularly limited, but is preferably 3 to 12, more preferably 4 to 6, and even more preferably 5. Examples of heteroatoms contained in the aliphatic heterocycle include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred.

[0042] In formula (1), R Ｚ２ represents an aliphatic hydrocarbon group which may have a substituent, an acyl group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or —Si(R Ｓｉ ) ３ R represents a group represented by the formula: Ｚ２ The aliphatic hydrocarbon group represented by the formula (I) may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group represented by the formula (I) may contain a halogen atom. In this specification, the expression "the aliphatic hydrocarbon group may contain an etheric oxygen atom" means that the aliphatic hydrocarbon group may contain a divalent linking group represented by -O- in the middle or at the end.

[0043] R Ｚ２Examples of the aliphatic hydrocarbon group represented by the formula (I) include linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups. The linear aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a vinyl group, an allyl group, an ethynyl group, and a propargyl group. A methyl group, an ethyl group, an n-propyl group, a vinyl group, an ethynyl group, or a propargyl group is preferred, a methyl group, an ethyl group, or an ethynyl group is more preferred, and a methyl group or an ethyl group is even more preferred. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, even more preferably 3 to 6 carbon atoms, and particularly preferably 3 or 4 carbon atoms. Specific examples include an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-butyloctyl group, a 2-hexyloctyl group, a 2-hexyldodecyl group, and a 2-octyldodecyl group, with an isopropyl group or a tert-butyl group being preferred. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, dicyclobutanyl, bicyclo[1.1.1]pentyl, and bicyclo[2.2.2]pentyl groups, with cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl being preferred, and cyclopropyl being more preferred. The aliphatic hydrocarbon group may have a halogen atom. Examples of the halogen atom that the aliphatic hydrocarbon group may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred. The aliphatic hydrocarbon group may have an ethereal oxygen atom.Examples of the aliphatic hydrocarbon group having an etheric oxygen atom include a methoxy group, an ethoxy group, an isopropoxy group, a cyclopropoxy group, and a methoxyethyl group. Examples of the substituent that the aliphatic hydrocarbon group may have include the substituents exemplified by the substituent W described above, and a substituent selected from the substituent group S described below is preferred, and a substituent selected from the substituent group T described below is more preferred.

[0044] R Ｚ２ The hydrocarbon group contained in the acyl group which may have a substituent, represented by the formula (I), may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. The aliphatic hydrocarbon group contained in the acyl group may be linear, branched, or cyclic. The number of carbon atoms contained in the aliphatic hydrocarbon group contained in the acyl group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, and particularly preferably 1 or 2. Specific examples thereof include linear aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, 1-ethylpentyl, 2,6-dimethylheptyl, 1-butylheptyl, 1-hexylheptyl, 1-hexylundecyl, and Examples of the acyl group include branched aliphatic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, dicyclobutanyl, bicyclo[1.1.1]pentyl, and bicyclo[2.2.2]pentyl groups, with methyl, ethyl, n-propyl, isopropyl, and tert-butyl being preferred, and methyl or ethyl being more preferred. The number of carbon atoms in the aromatic hydrocarbon group of the acyl group is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. Specific examples include phenyl, naphthyl, anthryl, pyrenyl, phenanthrenyl, and fluorenyl groups, with phenyl being preferred.

[0045] The number of carbon atoms in the acyl group is preferably 2 to 21, more preferably 2 to 11, even more preferably 2 to 5, and particularly preferably 2 or 3. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, and a benzoyl group, with an acetyl group or a propionyl group being preferred. The acyl group may have a halogen atom. Examples of the halogen atom that the acyl group may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred. Examples of the substituent that the acyl group may have include the substituents exemplified by the substituent W described above, with a substituent selected from the substituent group S described below being preferred, and a substituent selected from the substituent group T described below being more preferred.

[0046] R Ｚ２The aromatic ring group represented by the formula (I) which may have a substituent may be either a monocyclic or polycyclic ring. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The aromatic ring group preferably has 5 to 20 ring members, more preferably 5 to 12, and even more preferably 5 to 8. The aromatic ring group preferably has 30 or fewer carbon atoms, more preferably 20 or fewer, and even more preferably 10 or fewer. The lower limit is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more. Examples of heteroatoms contained in the aromatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred. As the aromatic ring group, for example, can be enumerated aromatic hydrocarbon ring group such as phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthrenyl group and fluorenyl group; pyridine ring group, pyrimidine ring group, pyridazine ring group, pyrazine ring group, triazine ring group, tetrazine ring group, quinoxaline ring group, pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, oxazole ring group, pyrazole ring group, thiazole ring group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, benzimidazole ring group, benzoxazole ring group and benzothiazole ring group, etc. aromatic heterocyclic group, can be enumerated phenyl group, thiophene ring group, furan ring group or pyridine ring group, can be enumerated phenyl group, thiophene ring group or pyridine ring group, can be enumerated phenyl group or thiophene ring group more preferred, can be enumerated phenyl group.As the substituent that can be possessed by the aromatic ring group, can be enumerated the substituent exemplified by the above-mentioned substituent W, can be enumerated hereinafter as the substituent selected from the substituent group S, can be enumerated hereinafter as the substituent selected from the substituent group T, can be enumerated hereinafter as the substituent selected from the substituent group T. When the aromatic ring group has a substituent, the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

[0047] R Ｚ２The aliphatic heterocyclic group represented by the formula (I) which may have a substituent may be either monocyclic or polycyclic. The number of ring members in the aliphatic heterocyclic group is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6 to 8. The number of carbon atoms in the aliphatic heterocyclic group is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 10. Examples of heteroatoms contained in the aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred. Examples of the aliphatic heterocyclic group include a pyrrolidine ring group, an oxolane ring group, a thiolane ring group, a piperidine ring group, a tetrahydrofuran ring group, a tetrahydropyran ring group, a thiane ring group, a piperazine ring group, a morpholine ring group, a quinuclidine ring group, a pyrrolidine ring group, an azetidine ring group, an oxetane ring group, an aziridine ring group, a dioxane ring group, a pentamethylene sulfide ring group, and a γ-butyrolactone ring group, with a piperidine ring group being preferred. Examples of the substituent that the aliphatic heterocyclic group may have include the substituents exemplified by the substituent W described above, with a substituent selected from the substituent group S described below being preferred, and a substituent selected from the substituent group T described below being more preferred. When the aliphatic heterocyclic group has a substituent, the number of the substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.

[0048] -Si(R Ｓｉ ) ３ In the group represented by Ｓｉ R each independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. Ｓｉ The optionally substituted aliphatic hydrocarbon group represented by the formula (I) may have a halogen atom or an etheric oxygen atom. Ｓｉ The definition and preferred embodiments of the optionally substituted aliphatic hydrocarbon group represented by R Ｚ２ and R Ｓｉ The definition and preferred embodiments of the optionally substituted aromatic ring group represented by R Ｚ２In particular, the aromatic ring group represented by -Si(R Ｓｉ ) ３ Examples of the group represented by the formula include —Si(R Ｓｉ２ ) ３ A group represented by the following formula is preferred. Ｓｉ２ R each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S described below, or an aromatic ring group which may have a substituent selected from the substituent group S described below. Ｓｉ２ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S may have a halogen atom or an etheric oxygen atom. Ｓｉ ) ３ Examples of the group represented by the formula include —Si(R Ｓｉ３ ) ３ A group represented by the following formula is more preferred. Ｓｉ３ each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the substituent group T described below, or an aromatic ring group which may have a substituent selected from the substituent group T described below. -Si(R Ｓｉ ) ３ Specific examples of the group represented by the formula (I) include a trimethylsilyl group, a triethylsilyl group, a dimethylisopropylsilyl group, a diethylisopropylsilyl group, a cyclohexyldimethylsilyl group, a dimethylphenylsilyl group, and a tert-butyldimethylsilyl group, and a trimethylsilyl group or a triethylsilyl group is preferred, and a trimethylsilyl group is more preferred.

[0049] The effect of the present invention is more excellent. Ｚ２is preferably a group selected from the substituent group R1. The substituent group R1 includes linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S described below, acyl groups having 2 to 5 carbon atoms, aromatic ring groups which may have a substituent selected from the substituent group S described below, aliphatic heterocyclic groups which may have a substituent selected from the substituent group S described below, and -Si(R Ｓｉ２ ) ３ In the substituent group R1, the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S may have a halogen atom or an etheric oxygen atom. Ｚ２ is more preferably a group selected from the substituent group R2. Substituent group R2: a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, an acyl group having 2 or 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the substituent group T described later, an aromatic ring group which may have a substituent selected from the substituent group T described later, an aliphatic heterocyclic group which may have a substituent selected from the substituent group T described later, and -Si(R Ｓｉ３ ) ３ A group represented by the formula:

[0050] The above-mentioned substituent group S and substituent group T will be described in detail below.

[0051] Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a halogen atom, and —Si(R Ｓｉ２ ) ３ A group represented by the formula:

[0052] Specific examples of the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms in the substituent group S include a methyl group, an ethyl group, an n-propyl group, a vinyl group, an allyl group, an ethynyl group, and a propargyl group, with a methyl group or an ethyl group being preferred, and a methyl group being more preferred. Specific examples of the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms in the substituent group S include an isopropyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group, with an isopropyl group or a tert-butyl group being preferred, and an isopropyl group being more preferred. The cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent group S may be either a monocyclic or a polycyclic ring, with a monocyclic ring being preferred. Specific examples of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, with a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group being preferred, and a cyclopropyl group being more preferred. The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the above-mentioned Substituent Group S (hereinafter also referred to as "aliphatic hydrocarbon groups in Substituent Group S") may contain a halogen atom. Examples of the halogen atom that the aliphatic hydrocarbon group in the above-mentioned Substituent Group S may contain include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred. The aliphatic hydrocarbon group in the above-mentioned Substituent Group S may contain an ethereal oxygen atom. Examples of the aliphatic hydrocarbon group in the group S of substituents having an etheric oxygen atom include a methoxy group, an ethoxy group, a methoxyethyl group, an isopropoxy group, and a cyclopropoxy group, with a methoxy group being preferred.

[0053] Examples of the halogen atom in the above-mentioned substituent group S include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom or a chlorine atom being preferred.

[0054] -Si(R Ｓｉ２ ) ３ In the group represented by Ｓｉ２R each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from Substituent Group S, or an aromatic ring group which may have a substituent selected from Substituent Group S. Ｓｉ２ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S may have a halogen atom or an etheric oxygen atom. Ｓｉ２ ) ３ The definition and preferred embodiments of the group represented by R Ｚ２ -Si(R Ｓｉ２ ) ３ It is the same as the group represented by the following formula:

[0055] The substituent selected from the substituent group S is preferably a substituent selected from the substituent group T in terms of achieving better effects of the present invention.

[0056] Substituent group T: a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, a halogen atom, and —Si(R Ｓｉ３ ) ３ A group represented by the formula:

[0057] Specific examples of the linear aliphatic hydrocarbon group having 1 or 2 carbon atoms in the substituent group T include a methyl group and an ethyl group, with a methyl group being preferred. Specific examples of the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms in the substituent group T include an isopropyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group, with an isopropyl group or a tert-butyl group being preferred, and an isopropyl group being more preferred. The cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms in the substituent group T may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. Specific examples of the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, with a cyclopropyl group being preferred.

[0058] Examples of the halogen atom in the above-mentioned substituent group T include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0059] -Si(R Ｓｉ３ ) ３ In the group represented by Ｓｉ３ each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the substituent group T, or an aromatic ring group which may have a substituent selected from the substituent group T. -Si(R Ｓｉ３ ) ３ The definition and preferred embodiments of the group represented by R Ｚ２ -Si(R Ｓｉ３ ) ３ It is the same as the group represented by the following formula:

[0060] In formula (1), A １ and A ２ each independently represents a group represented by formula (A-1).

[0061]

[0062] In formula (A-1), W １ represents an oxygen atom, a sulfur atom, and ═NRＷ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified above as the substituent W. Ｗ２ and R Ｗ３ each independently represents a cyano group, —SO ２ R Ｗ４ , -C(=O)OR Ｗ５ or -C(=O)R Ｗ６ Represents R Ｗ４ ~R Ｗ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Ｗ４ ~R Ｗ６ Examples of the substituent that may be present include the groups exemplified by the substituent W above. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and preferably has 1 to 3 carbon atoms. The aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and preferably a phenyl group. The aliphatic heterocyclic group preferably has 5 to 20 ring members, more preferably 5 to 12, and even more preferably 6 to 8. Examples of heteroatoms present in the aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and preferably a sulfur atom, an oxygen atom, or a nitrogen atom. Examples of the aliphatic heterocyclic ring constituting the aliphatic heterocyclic group include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydrofuran ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, a pyrrolidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, a pentamethylene sulfide ring, and γ-butyrolactone. １ is an oxygen atom, a sulfur atom, or ═CR Ｗ２ R Ｗ３ is preferred, an oxygen atom or a sulfur atom is more preferred, and an oxygen atom is even more preferred.

[0063] In formula (A-1), C １represents a ring containing at least two carbon atoms, which may have a substituent. １ The two carbon atoms contained in are the two carbon atoms specified in formula (A-1). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the two carbon atoms specified in the formula. The ring may be either an aromatic ring or a non-aromatic ring. The ring may be either a monocyclic or polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5. １ Among the carbon atoms constituting the ring represented by the formula (A-1), the carbon atom at the bonding position marked with * and W １ Carbon atoms other than the carbon atom bonded to may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0064] Examples of the substituent that the ring may have include the groups exemplified for the substituent W, and are preferably a halogen atom, an alkyl group, an aromatic ring group, or a silyl group, and more preferably a halogen atom or an alkyl group. The alkyl group may be linear, branched, or cyclic, and is preferably linear. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0065] Above C １The ring represented by the formula (I) is preferably a ring used as an acidic nucleus (for example, the acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, a 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione; (b) pyrazolinone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one; (c) isoxazolinone nucleus: for example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one; (d) oxindole nucleus: for example, 1-alkyl-2,3-dihydro-2-oxindole; (e) 2,4,6-trioxohexahydropyrimidine nucleus: for example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl, and 1,3-dibutyl, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl), and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl). (f) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-heteroarylrhodanines such as 3-(2-pyridyl)rhodanine. (g) 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazoledione nucleus): for example, 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone nucleus: for example, 3(2H)-thianaphthenone-1,1-dioxide. (i) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione.(j) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione. (k) thiazolin-4-one nucleus: for example, 4-thiazolinone and 2-ethyl-4-thiazolinone. (l) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione. (n) Imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one. (o) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione. (p) Benzothiophen-3(2H)-one nucleus: for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one and dioxobenzothiophen-3(2H)-one. (q) Indanone nucleus: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone and 3,3-dimethyl-1-indanone. (r) Benzofuran-3-(2H)-one nucleus: for example, benzofuran-3-(2H)-one. (s) 2,2-dihydrophenalene-1,3-dione nucleus, etc.

[0066] The effect of the present invention is more excellent. １ and A ２ are each preferably independently a group represented by formula (A-2).

[0067]

[0068] In formula (A-2), W ２ and W ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ , R Ｗ２ and R Ｗ３The definition and preferred embodiments of are as described above. ２ and W ３ is an oxygen atom, a sulfur atom or =C(CN) ２ is preferred, an oxygen atom or a sulfur atom is more preferred, and an oxygen atom is even more preferred. ２ and W ３ At least one of W is preferably an oxygen atom. ２ and W ３ is more preferably an oxygen atom.

[0069] In formula (A-2), C ２ represents a ring containing at least three carbon atoms, which may have a substituent. ２ The three carbon atoms contained in are the three carbon atoms specified in formula (A-2). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the three carbon atoms specified in the formula. The ring may be either an aromatic ring or a non-aromatic ring. The ring may be either a monocyclic or polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5. ２ Among the carbon atoms constituting the ring represented by the formula (A-2), the carbon atom at the bonding position marked with * and W ２ Or W ３ A carbon atom other than the carbon atom bonded to the ring C may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S). １ The substituents are the same as those that may be possessed by the group.

[0070] The effect of the present invention is more excellent. １ and A ２ are each independently more preferably a group represented by the following formula (C-1) or a group represented by the following formula (C-2), and further preferably a group represented by the following formula (C-2).

[0071]

[0072] In formula (C-1), X ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｘ１ or =CR Ｘ２ R Ｘ３ Represents R Ｘ１ represents a hydrogen atom or a substituent. Ｘ１ Examples of the substituent represented by R include the groups exemplified as the substituent W. Ｘ２ and R Ｘ３ each independently represents a cyano group, —SO ２ R Ｘ４ , -C(=O)OR Ｘ５ or -C(=O)R Ｘ６ Represents R Ｘ４ ~R Ｘ６ R each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Ｘ４ ~R Ｘ６ The definitions and preferred embodiments of each group represented by R Ｗ４ ~R Ｗ６ The same applies to each group represented by R Ｘ２ and R Ｘ３ At least one of R is preferably a cyano group, Ｘ２ and R Ｘ３ is more preferably a cyano group. ｃ１ and X ｃ２ is an oxygen atom, a sulfur atom or =C(CN) ２ is preferred, an oxygen atom or a sulfur atom is more preferred, and an oxygen atom is even more preferred. ｃ１ and X ｃ２Preferably, at least one of X is an oxygen atom, ｃ１ and X ｃ２ is more preferably an oxygen atom.

[0073] In formula (C-1), C ３ represents an aromatic ring which may have a substituent. The number of ring members in the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of ring members in the aromatic ring is the number including the two carbon atoms specified in the formula. The aromatic ring may be either a monocyclic or polycyclic ring. Furthermore, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred. The C ３ The aromatic ring represented by the formula (I) is as described above, and is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyridine ring, a thienothiophene ring, a benzothiophene ring, a benzofuran ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring, more preferably a benzene ring, a naphthalene ring, or a thiophene ring, and particularly preferably a benzene ring. Examples of the substituent that the aromatic ring may have include the groups exemplified by the substituent W, and an alkyl group or a halogen atom is preferred. The number of substituents that the aromatic ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.

[0074] In formula (C-2), X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｘ１ or =CR Ｘ２ R Ｘ３ Represents R Ｘ１ ~R Ｘ３ The definition and preferred embodiments of X are as described above. ｃ３ ~X ｃ５ is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom. ｃ３ ~X ｃ５ Preferably, at least two of the groups are oxygen atoms, and more preferably, all of the groups are oxygen atoms.

[0075] R ｃ１ and Rｃ２ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent W above, with an alkyl group or an aryl group being preferred, and an alkyl group being more preferred. The alkyl group may be linear, branched, or cyclic, with a linear group being preferred. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1. The aryl group may be either monocyclic or polycyclic, with a phenyl group being preferred. The phenyl group may further have a substituent, and examples of the substituent include the groups exemplified for the substituent W above.

[0076] In formula (1), A １ and A ２ is a group represented by formula (A-2), the specific compound is represented by the following formula (1-A2), and when it is a group represented by formula (C-1), the specific compound is represented by the following formula (1-C1), and A １ and A ２ is a group represented by formula (C-2), the specific compound is represented by the following formula (1-C2).

[0077]

[0078] The specific compound is preferably a compound represented by formula (1-A2), more preferably a compound represented by formula (1-C1) or formula (1-C2), and even more preferably a compound represented by formula (1-C2). In formulas (1-A2), (1-C1), and (1-C2), multiple groups represented by the same symbol may be the same or different, but are preferably the same.

[0079] Specific examples of the specific compound are shown below, but the present invention is not limited to these.

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] In the specific compounds exemplified above, A represents any of the following groups.

[0086]

[0087]

[0088]

[0089] The molecular weight of the specific compound is preferably 400 to 1,400, more preferably 480 to 1,000, and even more preferably 520 to 800. When the molecular weight is within the above range, the sublimation temperature of the specific compound is lowered, and it is presumed that the specific compound has excellent suitability for production.

[0090] The specific compound preferably has an ionization potential of −5.0 to −6.0 eV in a single film from the viewpoints of stability when used as a p-type organic semiconductor and matching of the energy level with an n-type organic semiconductor.

[0091] The maximum absorption wavelength of the specific compound is preferably in the wavelength range of 400 to 700 nm, more preferably in the range of 450 to 650 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the specific compound is insoluble in chloroform, the specific compound is vapor-deposited into a film state, and the value measured using the specific compound is regarded as the maximum absorption wavelength of the specific compound.

[0092] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, a photosensor, or a photovoltaic cell. The specific compound often functions as a dye in the photoelectric conversion film. The specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.

[0093] The specific compound may be purified as necessary. Examples of methods for purifying the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.

[0094] The content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound in terms of a single layer / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75% by volume, more preferably 10 to 50% by volume, and even more preferably 15 to 40% by volume. Only one type of specific compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.

[0095] <n-Type Organic Semiconductor> The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the specific compound. The n-type organic semiconductor is a compound different from the specific compound. The n-type organic semiconductor is an acceptor organic semiconductor material (compound) and refers to an organic compound that has the property of easily accepting electrons. In other words, the n-type organic semiconductor refers to the organic compound that has a larger electron affinity when two organic compounds are used in contact with each other. In other words, any organic compound can be used as the acceptor organic semiconductor as long as it is an organic compound with electron-accepting properties. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; condensed aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyridine ... 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives and oxadiazole derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; and the compounds described in paragraphs

[0056] to

[0057] of JP 2006-100767 A.

[0096] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred. For example, fullerene C ６０ , fullerene C ７０ , fullerene C ７６ , fullerene C ７８, fullerene C ８０ , fullerene C ８２ , fullerene C ８４ , fullerene C ９０ , fullerene C ９６ , fullerene C ２４０ , fullerene C ５４０ and mixed fullerenes. Examples of fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerenes. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. Preferred fullerene derivatives are the compounds described in JP-A-2007-123707.

[0097] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0098] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less or in the range of 500 to 600 nm.

[0099] The photoelectric conversion film preferably has a bulk heterostructure formed in a state in which a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in the photoelectric conversion film in which a specific compound and an n-type organic semiconductor are mixed and dispersed. The photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs

[0013] to

[0014] of JP 2005-303266 A.

[0100] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0101] When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (thickness of the n-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.

[0102] When the n-type organic semiconductor contains fullerenes, the content of the fullerenes relative to the total content of the n-type organic semiconductors (film thickness of fullerenes converted into a single layer / total film thickness of each n-type organic semiconductor converted into a single layer × 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. Fullerenes may be used singly or in combination of two or more types.

[0103] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor) x 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume. When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the p-type organic semiconductor) x 100) is preferably 10 to 75% by volume, more preferably 15 to 50% by volume. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and a p-type organic semiconductor that is included as desired. "Substantially" means that the total content of the specific compound, n-type organic semiconductor, and p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume.

[0104] <p-Type Organic Semiconductor> The photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the specific compound. The p-type organic semiconductor is a compound different from the specific compound. The p-type organic semiconductor is a donor organic semiconductor material (compound) and refers to an organic compound that has the property of easily donating electrons. In other words, the p-type organic semiconductor refers to the organic compound that has a smaller ionization potential when two organic compounds are used in contact with each other. The p-type organic semiconductor may be used alone or in combination of two or more types.

[0105] Examples of p-type organic semiconductors include triarylamine compounds (e.g., N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), compounds described in paragraphs

[0128] to

[0148] of JP-A No. 2011-228614, compounds described in paragraphs

[0052] to

[0063] of JP-A No. 2011-176259, compounds described in paragraphs

[0119] to

[0158] of JP-A No. 2011-225544, compounds described in paragraphs

[0119] to

[0158] of JP-A No. compounds described in paragraphs

[0044] to

[0051] of JP-A No. 2015-153910 and compounds described in paragraphs

[0086] to

[0090] of JP-A No. 2012-094660, etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b]thiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of JP 2018-014474 A, compounds described in paragraphs

[0043] to

[0045] of WO 2016 / 194630 A, compounds described in paragraphs

[0025] to

[0037] and

[0099] to

[0109] of WO 2017 / 159684 A, compounds described in paragraphs

[0029] to

[0034] of JP 2017-076766 A, compounds described in paragraphs

[0015] to

[0025] of WO 2018 / 207722 A, and compounds described in paragraph

[0045] of JP 2019-054228 A ] to

[0053] , compounds described in paragraphs

[0045] to

[0055] of WO2019 / 058995, compounds described in paragraphs

[0063] to

[0089] of WO2019 / 081416, compounds described in paragraphs

[0033] to

[0036] of JP2019-80052A, compounds described in paragraphs

[0044] to

[0054] of WO2019 / 054125, compounds described in paragraphs

[0041] to

[0046] of WO2019 / 093188, compounds described in paragraphs

[0034] to

[0037] of JP2019-050398A,The compounds of paragraphs

[0033] to

[0036] of JP-A No. 2018-206878, the compounds of paragraphs

[0038] of JP-A No. 2018-190755, the compounds of paragraphs

[0019] to

[0021] of JP-A No. 2018-026559, the compounds of paragraphs

[0031] to

[0056] of JP-A No. 2018-170487, the compounds of paragraphs

[0036] to

[0041] of JP-A No. 2018-166200 The compounds of paragraphs

[0055] to

[0082] of JP-A-2018-113425, paragraphs

[0041] to

[0050] , the compounds of paragraphs

[0044] to

[0048] of JP-A-2018-085430, the compounds of paragraphs

[0041] to

[0045] of JP-A-2018-056546, the compounds of paragraphs

[0042] to

[0049] of JP-A-2018-046267, the compounds of paragraphs

[0031] to [003 6] compounds, WO2018 / 016465 paragraphs

[0036] to

[0046] compounds described in, as well as JP-A-2020-010024 paragraphs

[0045] to

[0048] compounds, etc.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. Further, as p-type organic semiconductors, compounds described in JP-A-2022-123944, compounds described in JP-A-2022-122839, compounds described in JP-A-2022-120323, compounds described in JP-A-2022-120273, compounds described in JP-A-2022-115832, compounds described in JP-A-2022-108268, compounds described in JP-A-2023-005703, compounds described in JP-A-2022-100258,Examples of p-type organic semiconductors include compounds described in JP-A-2022-181226, JP-A-2022-27575, and JP-A-2021-163968. Examples of p-type organic semiconductors include compounds with a smaller ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are listed below.

[0106]

[0107]

[0108]

[0109]

[0110] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0111] When the photoelectric conversion film contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the photoelectric conversion film (thickness of the p-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.

[0112] The photoelectric conversion film containing the specific compound is a non-luminescent film and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode). A non-luminescent film means a film having a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less. The lower limit is often 0% or more.

[0113] <Dye> The photoelectric conversion film preferably contains a dye in addition to the specific compound. The dye is a compound different from the specific compound. The dye is preferably an organic dye. Examples of the organic dye include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, and acrylonitrile dyes. Examples of the dye include lysinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, cyanine dyes, metal complexes, imidazoquinoxaline dyes described in WO2020 / 013246, WO2022 / 168856, JP-A-2023-10305, and JP-A-2023-10299, acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and donor-acceptor-donor type dyes in which two donors are bonded to an acceptor. Among these, in terms of maximum absorption wavelength, cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred.

[0114] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and even more preferably in the wavelength range of 450 to 650 nm.

[0115] The content of the dye relative to the total content of the specific compound and the dye in the photoelectric conversion film (= (film thickness of the dye in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the dye in terms of a single layer)×100)) is preferably 5 to 75 vol%, more preferably 5 to 60 vol%, and still more preferably 5 to 50 vol%.

[0116] <Film formation method> Examples of the film formation method for the photoelectric conversion film include dry film formation methods. Examples of dry film formation methods include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and vacuum deposition methods are preferred. When forming the photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0117] The thickness of the photoelectric conversion film is preferably from 10 to 1,000 nm, more preferably from 50 to 800 nm, and even more preferably from 50 to 500 nm.

[0118] [Electrodes] The photoelectric conversion element preferably has electrodes. The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of conductive materials include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident through the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and nanocarbon materials such as carbon nanotubes and graphene. Of these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0119] Typically, when the conductive film is made thinner than a certain range, the resistance value often increases rapidly. In a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10,000 Ω / □, and there is a wide degree of freedom in the range of film thickness that can be reduced. Furthermore, the thinner the film thickness of the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher the light transmittance. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and enhances photoelectric conversion performance. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance that accompany a reduction in film thickness, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0120] Depending on the application, the lower electrode 11 may be made transparent or may be made non-transparent and reflect light. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, etc., tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.

[0121] The method for forming the electrodes can be appropriately selected depending on the electrode material. Specific examples include wet methods such as printing and coating; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD. When the electrode material is ITO, examples include electron beam methods, sputtering, resistance heating deposition, chemical reaction methods (such as the sol-gel method), and coating of a dispersion of indium tin oxide.

[0122] [Charge-blocking film: electron-blocking film, hole-blocking film] The photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge-blocking film. When the photoelectric conversion element has this film, the properties (quantum efficiency, response speed, etc.) of the resulting photoelectric conversion element are more excellent. Examples of the charge-blocking film include an electron-blocking film and a hole-blocking film.

[0123] <Electron Blocking Film> The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Polymer materials can also be used as the electron blocking film. Examples of polymer materials include polymers of phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and the like, and derivatives thereof.

[0124] The electron blocking film may be composed of multiple films. The electron blocking film may be composed of an inorganic material. In general, inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency. Examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0125] <Hole-Blocking Film> The hole-blocking film is an acceptor organic semiconductor material (compound), and the n-type organic semiconductors described above can be used. The hole-blocking film may be composed of multiple films.

[0126] Examples of methods for producing a charge blocking film include dry film formation and wet film formation. Examples of dry film formation include vapor deposition and sputtering. Vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition such as vacuum deposition being preferred. Examples of wet film formation include inkjet printing, spray printing, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with the inkjet method being preferred in terms of high-precision patterning.

[0127] The thickness of each of the charge blocking films (electron blocking film and hole blocking film) is preferably from 3 to 200 nm, more preferably from 5 to 100 nm, and even more preferably from 5 to 30 nm.

[0128] [Substrate] The photoelectric conversion element may further include a substrate. Examples of the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate. The substrate is usually positioned such that a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked in this order on the substrate.

[0129] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. The performance of photoelectric conversion materials may be significantly degraded in the presence of degrading factors such as water molecules. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of ceramics such as dense metal oxides, metal nitrides, or metal nitride oxides, or diamond-like carbon (DLC), which do not allow water molecules to penetrate. Examples of sealing layers include those described in paragraphs

[0210] to

[0215] of JP 2011-082508 A, the contents of which are incorporated herein by reference.

[0130] [Image capture element] An example of an application of a photoelectric conversion element is an image capture element. An image capture element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal and outputting the electrical signal pixel by pixel from the image capture element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0131] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, a photocell and an optical sensor, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged linearly or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.

[0132] [Compound] The present invention also includes inventions of specific compounds.

[0133] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0134] [Compounds used in photoelectric conversion film] The materials used in the photoelectric conversion film are shown below.

[0135] [Synthesis of Compound (1-1)] Compound (1-1) was synthesized according to the following scheme.

[0136]

[0137] Compound (1-1-1) (2.0 mmol), compound (1-1-2) (5.0 mmol), toluene (60 mL), and piperidine (0.02 mmol) were placed in a glass reaction vessel and reacted at 100°C for 2 hours under a nitrogen atmosphere. The precipitated solid was filtered, and the resulting solid was washed successively with tetrahydrofuran (THF), dimethylacetamide (DMAc), and THF, followed by purification by sublimation to obtain 1.4 mmol of compound (1-1) (yield 70%). The structure of compound (1-1) was confirmed by LDI-MS. LDI-MS (compound (1-1)): 562 (M ＋ )

[0138] The specific compounds used in the photoelectric conversion film other than the compound (1-1) were synthesized according to the synthesis method of the compound (1-1) above.

[0139] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for comparison are shown below. Note that compounds (1-1) to (1-28), compounds (2-1) to (2-8), compounds (3-1) to (3-7), compounds (4-1) to (4-6), and compounds (5-1) to (5-9) all fall under the specific compounds of the present invention, and compounds (C-1) to (C-11) all fall under comparative compounds for comparison.

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147] [n-type organic semiconductor] C60: fullerene (C ６０ )

[0148] [p-type organic semiconductor]

[0149]

[0150] [Pigment]

[0151]

[0152] [Evaluation] [Test X] <Preparation of Photoelectric Conversion Element (A)> Using the obtained compound, a photoelectric conversion element (A) having the configuration shown in FIG. 2 was prepared. Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Furthermore, with the temperature of the glass substrate controlled at 25° C., each specific compound or each comparative compound shown in Table 1 or Table 2 and an n-type organic semiconductor (fullerene (C ６０ )) and a p-type organic semiconductor shown in Table 1 or Table 2 were co-deposited by vacuum deposition at a predetermined ratio (specific compound: n-type organic semiconductor: p-type organic semiconductor = 1:1:1, thickness conversion). This resulted in a photoelectric conversion film 12 having a bulk heterostructure of 300 nm. The deposition rate of the photoelectric conversion film 12 was 1.0 Å / sec. Further, compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole-blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole-blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). A SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, and then aluminum oxide (Al) was deposited thereon by atomic layer chemical vapor deposition (ALCVD). ２ O ３ ) layer was formed to prepare each photoelectric conversion element (A).

[0153]

[0154] <Measurement of Dark Current> The dark current of each of the obtained photoelectric conversion elements (A) was measured by the following method. ５A voltage was applied so as to give an electric field strength of 100 nA / cm, and the current value in a dark place (dark current) was measured. As a result, in all photoelectric conversion elements (A), the dark current was 50 nA / cm. ２ It was confirmed that the dark current was sufficiently low.

[0155] <Evaluation of Quantum Efficiency (External Quantum Efficiency)> The quantum efficiency of each photoelectric conversion element (A) was evaluated by the following method. ５ A voltage was applied to achieve an electric field strength of 1000 VAC / cm. Subsequently, light was irradiated from the upper electrode (transparent conductive film) side to perform IPCE (incident photon-to-current conversion efficiency) measurement, and the photoelectric conversion efficiency (external quantum efficiency) values ​​at wavelengths of 460 nm and 600 nm were extracted. The photoelectric conversion efficiency was measured using a constant energy quantum efficiency measurement device manufactured by Optel. The irradiated light intensity was 50 μW / cm. ２ Using the photoelectric conversion efficiency of each photoelectric conversion element (A) obtained, the relative ratio of quantum efficiency was calculated at each wavelength according to formula (S1). The quantum efficiency was evaluated from the obtained values ​​according to the following evaluation criteria.

[0156] Formula (S1): Relative ratio of quantum efficiency = (photoelectric conversion efficiency of each photoelectric conversion element (A)) / (photoelectric conversion efficiency of photoelectric conversion element (A) of Comparative Example 1-10) Note that, when calculating the relative ratio, the values ​​of the photoelectric conversion efficiencies at the same wavelength were used as the numerator and denominator.

[0157] A: The relative ratio of quantum efficiency is 1.4 or more. B: The relative ratio of quantum efficiency is 1.2 or more and less than 1.4. C: The relative ratio of quantum efficiency is 1.0 or more and less than 1.2. D: The relative ratio of quantum efficiency is 0.8 or more and less than 1.0. E: The relative ratio of quantum efficiency is less than 0.8.

[0158] <Evaluation of response speed> The response speed of each photoelectric conversion element (A) was evaluated by the following method. ５A voltage was applied so that the intensity was 1000 V / cm. Then, the LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 580 nm was measured with an oscilloscope, and the rise time from 0% signal intensity to 97% signal intensity was measured. Using the rise time at a wavelength of 580 nm of each obtained photoelectric conversion element (A), the relative response speed was calculated according to formula (S2). From the obtained values, the response speed was evaluated according to the following evaluation criteria.

[0159] Equation (S2): Relative response speed = (rise time of each photoelectric conversion element (A)) / (rise time of photoelectric conversion element (A) of Comparative Examples 1-10)

[0160] A: Relative response speed is less than 0.5 B: Relative response speed is 0.5 or more and less than 1.0 C: Relative response speed is 1.0 or more and less than 1.5 D: Relative response speed is 1.5 or more and less than 2.5 E: Relative response speed is 2.5 or more

[0161] <Evaluation of Dependence of Response Speed ​​on Electric Field Strength> The dependence of response speed on electric field strength was evaluated for each photoelectric conversion element (A) by the following method. In the <Evaluation of Response Speed>, a voltage of 7.5×10 ４ The same procedure was followed except that the applied voltage was changed to 7.5 × 10 V / cm. ４ The rise time at a wavelength of 580 nm was measured for each photoelectric conversion element (A) at each applied voltage, and the relative ratio of the rise times was calculated according to formula (S3). The response speed was evaluated for its electric field strength dependency from the obtained values ​​according to the following evaluation criteria.

[0162] Equation (S3): Relative ratio of rise time = (applied voltage 7.5 × 10 ４ V / cm) / (applied voltage 2.0×10 ５ V / cm)

[0163] A: The relative ratio of the rise time is less than 2.0. B: The relative ratio of the rise time is 2.0 or more and less than 3.0. C: The relative ratio of the rise time is 3.0 or more and less than 4.0. D: The relative ratio of the rise time is 4.0 or more and less than 5.0. E: The relative ratio of the rise time is 5.0 or more.

[0164] <Evaluation of Manufacturing Suitability> The manufacturing suitability of the photoelectric conversion elements having the configurations of each Example and Comparative Example was evaluated by the following method. Photoelectric conversion elements (B) of each Example or Comparative Example were prepared in the same manner as the photoelectric conversion element (A), except that the deposition rate of the photoelectric conversion film 12 was set to 3.0 Å / sec. Next, the photoelectric conversion efficiency of the obtained photoelectric conversion element (B) was measured in the same manner as in <Evaluation of Quantum Efficiency (External Quantum Efficiency)>. Using the measured values ​​of the photoelectric conversion efficiencies at 600 nm of the photoelectric conversion element (A) and photoelectric conversion element (B) having the same configuration as the Example or Comparative Example, the relative ratio B / A of the photoelectric conversion efficiencies was calculated according to formula (S4). From the obtained values, the manufacturing suitability was evaluated according to the following evaluation criteria. The closer the value of the relative ratio B / A is to 1, the less the characteristics of the photoelectric conversion element are likely to deteriorate when the deposition rate is increased, i.e., the better the manufacturing suitability.

[0165] Equation (S4): Relative ratio of photoelectric conversion efficiency B / A=(photoelectric conversion efficiency of photoelectric conversion element (B)) / (photoelectric conversion efficiency of photoelectric conversion element (A))

[0166] A: The relative ratio B / A is 0.90 or more. B: The relative ratio B / A is 0.85 or more and less than 0.90. C: The relative ratio B / A is 0.80 or more and less than 0.85. D: The relative ratio B / A is 0.75 or more and less than 0.80. E: The relative ratio B / A is less than 0.75.

[0167] <Results> The evaluation results are shown in Tables 1 and 2 below. In the tables, in the "Formula (1)" column, when the specific compound is a compound represented by formula (1), it is marked with "A", and in other cases it is marked with "B". １ The column "" indicates that the specific compound is X in formula (1). １ In the table, when "X" is an oxygen atom, it is classified as "A", and when it is not, it is classified as "B". １ , X ３ The column "" indicates that the specific compound is X in formula (1). １ and X３ In the table, the column "Formula (A-2)" indicates that the specific compound is a compound in which A in formula (1) is an oxygen atom. １ and A ２ In the table, the column "Formula (C-1), Formula (C-2)" indicates that the specific compound is a group represented by A in formula (1). １ and A ２ In the table, the column "R1" indicates that the specific compound is a group represented by formula (C-1), "C-1" indicates that the specific compound is a group represented by formula (C-2), "C-2" indicates that the specific compound is a group represented by formula (C-2), and "B" indicates that the specific compound is a group represented by formula (C-1). Ｚ２ In the table, the column "R2" indicates that the specific compound is a compound in which R Ｚ２ is a group selected from the substituent group R2, the compound is designated as "A", and in other cases the compound is designated as "B".

[0168]

[0169]

[0170] From the results shown in Tables 1 and 2, it was confirmed that the photoelectric conversion element of the present invention has excellent quantum efficiency and excellent manufacturability. It was also confirmed that the photoelectric conversion element of the present invention has excellent response speed and electric field strength dependency of the response speed.

[0171] By comparing Examples 1-30 to 1-44 and Examples 1-51 to 1-59 with other Examples, it is clear that in formula (1), X １ When X is an oxygen atom, the manufacturability is better, １ and X ３ It was confirmed that when A is an oxygen atom, the manufacturability is further improved. １ and A ２ is a group represented by formula (A-2), the response speed and the electric field strength dependency of the response speed are more excellent, １ and A ２It was confirmed that when A is a group represented by formula (C-1) or a group represented by formula (C-2), the quantum efficiency is further improved. １ and A ２ It was confirmed that when R is a group represented by formula (C-2), the production efficiency is superior. Ｚ２ is a group selected from the above-mentioned substituent group R1, the quantum efficiency, response speed, the electric field strength dependency of the response speed, and production suitability are more excellent, and when it is a group selected from the substituent group R2, the production suitability is even more excellent.

[0172] [Test Y] <Preparation of Photoelectric Conversion Element (C)> Photoelectric conversion elements (C) of each of the Examples and Comparative Examples were prepared in the same manner as in Test X, except that each specific compound or each comparative compound shown in Table 3, C60 as an n-type organic semiconductor, Compound P-1 as a p-type organic semiconductor, and a compound shown in Table 3 as a dye were co-deposited by a vacuum deposition method in a predetermined ratio (specific compound:dye:p-type organic semiconductor:n-type organic semiconductor=1:1:2:2, in terms of thickness) to form a photoelectric conversion film 12 having a thickness of 300 nm.

[0173] <Dark Current> The dark current of the obtained photoelectric conversion element (C) was measured in the same procedure as in <Measurement of Dark Current> in [Test X]. As a result, the dark current of each photoelectric conversion element (C) was 50 nA / cm ２ It was confirmed that the dark current was sufficiently low.

[0174] <Evaluation of quantum efficiency (external quantum efficiency)> The photoelectric conversion efficiency of the obtained photoelectric conversion element (C) at wavelengths of 460 nm and 600 nm was calculated using the same procedure as in <Evaluation of quantum efficiency (external quantum efficiency)> in [Test X]. Using the photoelectric conversion efficiency of each photoelectric conversion element (C), the relative ratio of quantum efficiency at each wavelength was calculated according to formula (S5). From the obtained values, the quantum efficiency was evaluated according to the following evaluation criteria.

[0175] Equation (S5): Relative ratio of quantum efficiency = (photoelectric conversion efficiency of each photoelectric conversion element (C)) / (photoelectric conversion efficiency of photoelectric conversion element (C) of Comparative Example 2-10)

[0176] AA: The relative ratio of quantum efficiency is 1.6 or more. A: The relative ratio of quantum efficiency is 1.4 or more and less than 1.6. B: The relative ratio of quantum efficiency is 1.2 or more and less than 1.4. C: The relative ratio of quantum efficiency is 1.0 or more and less than 1.2. D: The relative ratio of quantum efficiency is 0.8 or more and less than 1.0. E: The relative ratio of quantum efficiency is less than 0.8.

[0177] <Evaluation of response speed> The rise time of the obtained photoelectric conversion element (C) at a wavelength of 580 nm was measured using the same procedure as in <Evaluation of response speed> of [Test X]. Using the rise time of each obtained photoelectric conversion element (C) at a wavelength of 580 nm, the relative response speed was calculated according to formula (S6). From the obtained value, the response speed was evaluated according to the following evaluation criteria.

[0178] Equation (S6): Relative response speed = (rise time of each photoelectric conversion element (C)) / (rise time of photoelectric conversion element (C) of Comparative Example 2-10)

[0179] A: Relative response speed is less than 0.5 B: Relative response speed is 0.5 or more and less than 1.0 C: Relative response speed is 1.0 or more and less than 1.5 D: Relative response speed is 1.5 or more and less than 2.5 E: Relative response speed is 2.5 or more

[0180] <Evaluation of Dependence of Response Speed ​​on Electric Field Strength> The dependency of response speed on electric field strength was evaluated for each photoelectric conversion element (C) by the following method. ４ V / cm and applied voltage 2.0 x 10 ５ The rise time at a wavelength of 580 nm was measured for each photoelectric conversion element (C) at each applied voltage, and the relative ratio of the rise times was calculated according to formula (S7). The response speed was evaluated for its electric field strength dependency based on the following evaluation criteria.

[0181] Equation (S7): Relative ratio of rise time = (applied voltage 7.5 × 10 ４ V / cm) / (applied voltage 2.0×10 ５V / cm)

[0182] A: The relative ratio of the rise time is less than 2.0. B: The relative ratio of the rise time is 2.0 or more and less than 3.0. C: The relative ratio of the rise time is 3.0 or more and less than 4.0. D: The relative ratio of the rise time is 4.0 or more and less than 5.0. E: The relative ratio of the rise time is 5.0 or more.

[0183] <Evaluation of manufacturing suitability> The manufacturing suitability of the photoelectric conversion elements having the configurations of each Example and Comparative Example was evaluated by the following method. Photoelectric conversion elements (D) of each Example or Comparative Example were prepared in the same procedure as for the photoelectric conversion element (C), except that the deposition rate of the photoelectric conversion film 12 was set to 3.0 Å / sec. Next, the photoelectric conversion efficiency of the obtained photoelectric conversion element (D) was measured in the same manner as in <Evaluation of quantum efficiency (external quantum efficiency)>. Using the measured values ​​of the photoelectric conversion efficiency at 600 nm of the photoelectric conversion element (C) and photoelectric conversion element (D) having the same configuration as the Example or Comparative Example, the relative ratio D / C of the photoelectric conversion efficiency was calculated according to formula (S8). From the obtained value, the manufacturing suitability was evaluated according to the following evaluation criteria. The closer the value of the relative ratio D / C is to 1, the less the characteristics of the photoelectric conversion element are likely to deteriorate when the deposition rate is increased, i.e., the better the manufacturing suitability.

[0184] Equation (S8): Relative ratio of photoelectric conversion efficiency D / C=(photoelectric conversion efficiency of photoelectric conversion element (D)) / (photoelectric conversion efficiency of photoelectric conversion element (C))

[0185] A: The relative ratio D / C is 0.90 or more. B: The relative ratio D / C is 0.85 or more and less than 0.90. C: The relative ratio D / C is 0.80 or more and less than 0.85. D: The relative ratio D / C is 0.75 or more and less than 0.80. E: The relative ratio D / C is less than 0.75.

[0186] <Results> The evaluation results are shown in Table 3. In Table 3, "Formula (1)", "X １ "," "X １ , X ３ "," "Formula (A-2)," "Formula (C-1), Formula (C-2)," "R1," and "R2" columns are the same as in Tables 1 and 2.

[0187]

[0188] From the results shown in Table 3 above, it was confirmed that the photoelectric conversion element having the configuration of Test Y of the present invention has excellent effects of the present invention, response speed, and electric field strength dependence of the response speed for light with a wavelength of 460 nm or 600 nm.

[0189] By comparing Examples 2-7 to 2-14 and 2-20 to 2-28 with other Examples, it is clear that in formula (1), X １ When X is an oxygen atom, the manufacturability is better, １ and X ３ It was confirmed that when A is an oxygen atom, the manufacturability is further improved. １ and A ２ is a group represented by formula (A-2), the response speed and the electric field strength dependency of the response speed are more excellent, １ and A ２ It was confirmed that when R is a group represented by formula (C-1) or a group represented by formula (C-2), the quantum efficiency is further improved. Ｚ２ is a group selected from the above-mentioned substituent group R1, it has been confirmed that the quantum efficiency, response speed, the electric field strength dependency of the response speed, and the manufacturing suitability are more excellent.

[0190] 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film

Claims

1. A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, The photoelectric conversion element, wherein the photoelectric conversion film contains a compound represented by formula (1): 【Chemical 1】 In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. X １ ~X ３ each independently represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom. １ ~X ３ At least one of these is an oxygen atom. Z １ ~Z ６ are each independently -CR Ｚ１ = or -N=. Ｚ１ represents a hydrogen atom or a substituent. １ ~Z ６ At least one of the groups is -CR Ｚ２ = R Ｚ２ represents an aliphatic hydrocarbon group which may have a substituent, an acyl group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or —Si(R Ｓｉ ) ３ represents a group represented by the formula: R Ｚ２ The aliphatic hydrocarbon group represented by the formula (I) may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group represented by the following formula may have a halogen atom. R Ｓｉ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. R Ｓｉ The aliphatic hydrocarbon group represented by the formula (I) may have a halogen atom or an etheric oxygen atom. Z １ and Z ２ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ３ and Z ４ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ５ and Z ６ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring. A １ and A ２ each independently represents a group represented by formula (A-1). In formula (A-1), C １ represents a ring containing at least two carbon atoms which may have a substituent. W １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ represents a hydrogen atom or a substituent. Ｗ２ and R Ｗ３ each independently represents a cyano group, —SO ２ R Ｗ４ , -COOR Ｗ５ or -COR Ｗ６ Represents R Ｗ４ , R Ｗ５ and R Ｗ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. * indicates the bond position.

2. X １ The photoelectric conversion element according to claim 1 , wherein is an oxygen atom.

3. X １ and X ３ The photoelectric conversion element according to claim 1 , wherein is an oxygen atom.

4. 2. The photoelectric conversion element according to claim 1, wherein the group represented by formula (A-1) is a group represented by formula (A-2). 【Chemistry 2】 In formula (A-2), C ２ represents a ring containing at least three carbon atoms which may have a substituent. W ２ and W ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ , R Ｗ２ and R Ｗ３ are R in the formula (1), respectively. Ｗ１ , R Ｗ２ and R Ｗ３ is synonymous with. * indicates the bond position.

5. 2. The photoelectric conversion element according to claim 1, wherein the group represented by formula (A-1) is a group represented by formula (C-1) or a group represented by formula (C-2). 【Chemistry 3】 In formula (C-1), X ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ , R Ｗ２ and R Ｗ３ are R in the formula (1), respectively. Ｗ１ , R Ｗ２ and R Ｗ３ is synonymous with. C ３ represents an aromatic ring which may have a substituent. * indicates the bond position. In formula (C-2), X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ , R Ｗ２ and R Ｗ３ are R in the formula (1), respectively. Ｗ１ , R Ｗ２ and R Ｗ３ is synonymous with. R ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent. * indicates the bond position.

6. R Ｚ２ is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from Substituent Group S, an acyl group having 2 to 5 carbon atoms, an aromatic ring group which may have a substituent selected from Substituent Group S, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group S, or -Si(R Ｓｉ２ ) ３ The photoelectric conversion element according to any one of claims 1 to 5, wherein the group is represented by the formula: R Ｚ２ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group having 2 to 5 carbon atoms represented by the following formula may have a halogen atom. Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a halogen atom, and —Si(R Ｓｉ２ ) ３ A group represented by the formula: The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent group S may have a halogen atom or an etheric oxygen atom. R Ｓｉ２ each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned Substituent Group S, or an aromatic ring group which may have a substituent selected from the above-mentioned Substituent Group S. R Ｓｉ２ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S may have a halogen atom or an etheric oxygen atom.

7. R Ｚ２ is a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, an acyl group having 2 or 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, an aromatic ring group which may have a substituent selected from Substituent Group T, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group T, or -Si(R Ｓｉ３ ) ３ The photoelectric conversion element according to any one of claims 1 to 5, wherein the group is represented by the formula: Substituent group T: a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, a halogen atom, and —Si(R Ｓｉ３ ) ３ A group represented by the formula: R Ｓｉ３ each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned substituent group T, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group T.

8. the photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) and the n-type organic semiconductor.

9. The photoelectric conversion element according to claim 8 , wherein the n-type organic semiconductor comprises a fullerene selected from the group consisting of fullerenes and derivatives thereof.

10. The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion film further contains a p-type organic semiconductor.

11. The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion film further contains a dye.

12. 6. The photoelectric conversion element according to claim 1, further comprising one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

13. An imaging device comprising the photoelectric conversion element according to any one of claims 1 to 5.

14. An optical sensor comprising the photoelectric conversion element according to any one of claims 1 to 5.

15. A compound represented by formula (1): 【Chemistry 4】 In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. X １ ~X ３ each independently represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom. １ ~X ３ At least one of these is an oxygen atom. Z １ ~Z ６ are each independently -CR Ｚ１ = or -N=. Ｚ１ represents a hydrogen atom or a substituent. １ ~Z ６ At least one of the groups is -CR Ｚ２ = R Ｚ２ represents an aliphatic hydrocarbon group which may have a substituent, an acyl group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or —Si(R Ｓｉ ) ３ represents a group represented by the formula: R Ｚ２ The aliphatic hydrocarbon group represented by the formula (I) may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group represented by the following formula may have a halogen atom. R Ｓｉ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. R Ｓｉ The aliphatic hydrocarbon group represented by the formula (I) may have a halogen atom or an etheric oxygen atom. Z １ and Z ２ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ３ and Z ４ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring, Z ５ and Z ６ Ga-CR Ｚ２ If =, then two R Ｚ２ may be bonded to each other to form a ring. A １ and A ２ each independently represents a group represented by formula (A-1). In formula (A-1), C １ represents a ring containing at least two carbon atoms which may have a substituent. W １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ represents a hydrogen atom or a substituent. Ｗ２ and R Ｗ３ each independently represents a cyano group, —SO ２ R Ｗ４ , -COOR Ｗ５ or -COR Ｗ６ Represents R Ｗ４ , R Ｗ５ and R Ｗ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. * indicates the bond position.

16. X １ The compound of claim 15 , wherein is an oxygen atom.

17. X １ and X ３ The compound of claim 15 , wherein is an oxygen atom.

18. The compound according to claim 15, wherein the group represented by formula (A-1) is a group represented by formula (A-2): 【Chemistry 5】 In formula (A-2), C ２ represents a ring containing at least three carbon atoms which may have a substituent. W ２ and W ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ , R Ｗ２ and R Ｗ３ are R in the formula (1), respectively. Ｗ１ , R Ｗ２ and R Ｗ３ is synonymous with. * indicates the bond position.

19. The compound according to claim 15, wherein the group represented by formula (A-1) is a group represented by formula (C-1) or a group represented by formula (C-2). 【Chemistry 6】 In formula (C-1), X ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ , R Ｗ２ and R Ｗ３ are R in the formula (1), respectively. Ｗ１ , R Ｗ２ and R Ｗ３ is synonymous with. C ３ represents an aromatic ring which may have a substituent. * indicates the bond position. In formula (C-2), X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ１ or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ , R Ｗ２ and R Ｗ３ are R in the formula (1), respectively. Ｗ１ , R Ｗ２ and R Ｗ３ is synonymous with. R ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent. * indicates the bond position.

20. R Ｚ２ is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from Substituent Group S, an acyl group having 2 to 5 carbon atoms, an aromatic ring group which may have a substituent selected from Substituent Group S, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group S, or -Si(R Ｓｉ２ ) ３ The compound according to any one of claims 15 to 19, wherein the compound represents a group represented by R Ｚ２ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S may have a halogen atom or an etheric oxygen atom. Ｚ２ The acyl group having 2 to 5 carbon atoms represented by the following formula may have a halogen atom. Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a halogen atom, and —Si(R Ｓｉ２ ) ３ A group represented by the formula: The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent group S may have a halogen atom or an etheric oxygen atom. R Ｓｉ２ each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned Substituent Group S, or an aromatic ring group which may have a substituent selected from the above-mentioned Substituent Group S. R Ｓｉ２ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S may have a halogen atom or an etheric oxygen atom.

21. R Ｚ２ is a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, an acyl group having 2 or 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, an aromatic ring group which may have a substituent selected from Substituent Group T, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group T, or -Si(R Ｓｉ３ ) ３ The compound according to any one of claims 15 to 19, wherein the compound represents a group represented by Substituent group T: a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, a halogen atom, and —Si(R Ｓｉ３ ) ３ A group represented by the formula: R Ｓｉ３ each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned substituent group T, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group T.

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