Photoelectric conversion element, imaging element, method for manufacturing imaging element, optical sensor, and compound

Abstract

The present invention provides: a photoelectric conversion element having excellent quantum efficiency for green and red light and low electric field strength dependency on responsiveness; and an imaging element, a method for manufacturing an imaging element, an optical sensor, and a compound. This photoelectric conversion element has 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 (1-1) or formula (1-2).

Description

Photoelectric conversion element, imaging element, imaging element manufacturing method, optical sensor, compound

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

[0002] In recent years, development of elements having a photoelectric conversion film as an organic electronic device has progressed. For example, Patent Document 1 discloses a photoelectric conversion element, an imaging element, and an electronic device that contain a compound having a specific structure represented by Formula (1) as a photoelectric conversion element that exhibits excellent external quantum efficiency and responsiveness to light of any of wavelengths in the red wavelength region, the green wavelength region, and the blue wavelength region.

[0003] International Publication No. 2021 / 221032

[0004] On the other hand, with the demand for improved performance of image sensors, optical sensors, and the like, there is a demand for photoelectric conversion elements that exhibit excellent characteristics. The characteristics required of a photoelectric conversion element include, for example, excellent quantum efficiency for green-red light and small electric field strength dependence of responsiveness to green-red light. In response to such demands, the present inventors fabricated and investigated a photoelectric conversion element using the compound disclosed in Patent Document 1, and found that the electric field strength dependence of responsiveness to green-red light needed to be improved. The above-mentioned green-red light refers to light with a wavelength of 550 to 650 nm.

[0005] Therefore, an object of the present invention is to provide a photoelectric conversion element that has excellent quantum efficiency for green and red light and small electric field strength dependency of response. Another object of the present invention is to provide an imaging element, a manufacturing method of 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 the formula (1-1) or the formula (1-2) described later. ２is a ring having at least one >C=X in the ring, or a ring having at least one acyl group. ２ and X ４ are each independently -CR Ｃ =. [4] The photoelectric conversion element according to any one of [1] to [3], wherein the compound is a compound represented by formula (1-1). [5] The photoelectric conversion element according to any one of [1] to [4], wherein A is a group represented by formula (A-1) above. [6] The photoelectric conversion element according to any one of [1] to [5], wherein A is a group represented by formula (A-3) described below. [7] The photoelectric conversion element according to any one of [1] to [6], wherein A is a group represented by formula (C-1) or formula (C-2) described below. [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 wherein the photoelectric conversion film has a bulk heterostructure formed by mixing the compound and the n-type organic semiconductor. [9] The photoelectric conversion element according to [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 [1] to [9], wherein the photoelectric conversion film further comprises a p-type organic semiconductor.

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

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

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

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

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

[12] .

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

[12] .

[15] A method for manufacturing an imaging element, comprising a step of manufacturing the photoelectric conversion element according to any one of [1] to

[12] .

[16] A compound represented by the formula (1-1) or the formula (1-2) described later. ２is a ring having at least one >C=X in the ring, or a ring having at least one acyl group. ２ and X ４ are each independently -CR Ｃ =.

[19] The compound according to any one of

[16] to

[18] , wherein the compound is a compound represented by the above formula (1-1).

[20] The compound according to any one of

[16] to

[19] , wherein A is a group represented by the above formula (A-1).

[21] The compound according to any one of

[16] to

[20] , wherein A is a group represented by the below-mentioned formula (A-3).

[22] The compound according to any one of

[16] to

[21] , wherein A is a group represented by the below-mentioned formula (C-1) or the below-mentioned formula (C-2).

[0008] According to the present invention, a photoelectric conversion element having excellent quantum efficiency for green and red light and small electric field strength dependency of response can be provided. Furthermore, according to the present invention, an imaging element, a manufacturing method of an imaging element, an optical sensor, and a compound related to the photoelectric conversion element can be provided.

[0009] 1 is a schematic cross-sectional view illustrating 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] The meaning of each description in this specification is as follows. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In this specification, a hydrogen atom may be a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom, etc.).

[0012] 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.

[0013] In this specification, with respect to a compound having an asymmetric atom, the general formula or structural formula representing the compound may be described without distinguishing between stereoisomers for convenience. Even in such a case, unless otherwise specified, the form of the compound is not limited to any one form, and may be any one form or a mixture. For example, unless otherwise specified, a compound having an asymmetric carbon atom may be either an S-form or an R-form, or a mixture thereof.

[0014] In this specification, unless otherwise specified, * in a formula represents a bonding position. The bonding direction of a divalent group (e.g., -CO-O-, etc.) in this specification 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".

[0015] In this specification, when there are multiple substituents, linking groups, etc. (hereinafter also referred to as "substituents, etc.") represented by specific symbols, or when multiple substituents, etc. are specified at the same time, it 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. In this specification, unless otherwise specified, "substituents" include, for example, groups exemplified as the substituent W described below.

[0016] (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 heteroaryl group, or an aliphatic 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 aryl ... Examples of the substituent W include an alkyloxy group, a primary, secondary, or tertiary amino group (including an anilino group), an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a carboxy group, a phosphate group, a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, and a boronic acid group. 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 a carbon atom, 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 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 has no primary amino groups.

[0017] 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. Furthermore, in this specification, unless otherwise specified, 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 t-butyl group, an n-hexyl group, a cyclopropyl group, and a cyclopentyl group. Furthermore, 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 3 to 18 carbon atoms, more preferably having 4 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom) is preferred.

[0018] 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.

[0019] 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.

[0020] 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, etc.). 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, etc.) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6, etc.) 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, an indole 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 naphtho[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.

[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 heterocycle 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 heterocycle among the above-mentioned aromatic rings. In the optionally substituted aromatic ring, 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 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 structure that is not aromatic, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle. Examples of the aliphatic hydrocarbon ring include cycloalkane, cycloalkene, and cycloalkyne. As used herein, the term "aliphatic heterocyclic group" refers to, for example, a group obtained by removing one hydrogen atom from the aliphatic heterocycle. As used herein, the number of ring members in the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 6 to 8. 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 heterocycle constituting the aliphatic heterocyclic group include a pyrrolidine ring, an oxolane ring (tetrahydrofuran ring), a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring (pentamethylene sulfide 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.

[0023] [Photoelectric Conversion Element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1-1) or formula (1-2) (hereinafter also referred to as a "specific compound").

[0024] Although the reason why the photoelectric conversion element having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. 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 one described below, it is still within the scope of the present invention. The specific compound is a so-called DA-type dye compound having a donor moiety (D) and an acceptor moiety (A). Because the specific compound has a predetermined donor structure and acceptor structure, excessive aggregation between the specific compounds and carrier trapping due to local dipoles are suppressed in the photoelectric conversion film. As a result, efficient charge separation can be achieved even at low electric field strength, and carriers can move efficiently, which is presumably why the effects of the present invention are achieved. Hereinafter, superior effects of at least one of the quantum efficiency for green-red light and the electric field strength dependence of responsiveness of the photoelectric conversion element of the present invention are also referred to as "excellent effects of the present invention."

[0025] 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.

[0026] 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.

[0027] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film.

[0028] <Specific Compound> The photoelectric conversion film contains a compound (specific compound) represented by formula (1-1) or formula (1-2). In terms of achieving better effects of the present invention, the specific compound is preferably a compound represented by formula (1-1).

[0029]

[0030] In formula (1-1), Ar １ is a ring having at least one >C=X in the ring (hereinafter referred to as "ring C Ｘ "), or a ring having at least one acyl group (hereinafter referred to as "ring C Ａ ") is also called.

[0031] Ring C Ｘ "having >C=X in the ring" means that the carbon atom in >C=X is not included in the ring C Ｘ Ring C refers to a ring member atom constituting the ring. Ｘ The number of >C=X in the formula (I) is preferably 1 to 5, more preferably 1 or 2, and even more preferably 2. X is an oxygen atom, a sulfur atom, or a ═NR Ｑ１ , or =CR Ｑ２ R Ｑ３ X is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.Ｘ When there are two or more >C=X, it is preferable that all of the multiple Xs are oxygen atoms.

[0032] =NR Ｑ１ Medium, R Ｑ１ represents a hydrogen atom or a substituent. Ｑ１ Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W above, and among these, 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 is preferred. Examples of the substituent which the aliphatic hydrocarbon group, aromatic ring group, and aliphatic heterocyclic group may have include the groups exemplified for the substituent W above.

[0033] Examples of the aliphatic hydrocarbon group in the aliphatic hydrocarbon group which may have a substituent include a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms. The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. The branched-chain aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 7, and even more preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic, but is preferably monocyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 8, and even more preferably 3 to 6.

[0034] The aromatic ring group in the aromatic ring group which may have a substituent may be either an aromatic hydrocarbon group (aryl group) or an aromatic heterocyclic group (heteroaryl group), with an aryl group being preferred. The aromatic ring group may be either a monocyclic or polycyclic ring. The number of ring atoms in the aromatic ring group is preferably 5 to 15, more preferably 5 to 10, and even more preferably 5 to 6. The number of carbon atoms in the aromatic ring group (the number of carbon atoms including the carbon atoms in the substituent) is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 12. 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. Specific examples of the aromatic ring group are as described above, and are preferably a phenyl group, a biphenyl group, a naphthyl group, a thiophene ring group, a furan ring group, a thiazole ring group, an oxazole ring group, a benzofuran ring group, a benzothiophene ring group, a thienothiophene ring group, a pyridine ring group, or a pyrimidine ring group, more preferably a phenyl group or a thiophene ring group, and even more preferably a phenyl group. The aromatic ring group may have a substituent. The number of substituents that the aromatic ring group may have is preferably 1 to 6, more preferably 1 to 3. Among these, the substituent that the aromatic ring group may have is preferably a cyano group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a halogen atom such as a chlorine atom.

[0035] The number of ring members in the aliphatic heterocyclic group which may have a substituent is preferably 5 to 20, more preferably 5 to 12, and still more preferably 5 to 8. The number of carbon atoms in the aliphatic heterocyclic group is preferably 1 to 20. 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, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferred.

[0036] =CR Ｑ２ R Ｑ３ Medium, R Ｑ２ and R Ｑ３ each independently represents a cyano group, —SO ２ R Ｑ４ , -COOR Ｑ５ , or -CORＱ６ Represents R Ｑ４ ~R Ｑ６ 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. Specific examples and preferred embodiments of the aliphatic hydrocarbon group which may have a substituent, the aromatic ring group which may have a substituent, and the aliphatic heterocyclic group which may have a substituent are Ｑ１ The aliphatic hydrocarbon group which may have a substituent, the aromatic ring group which may have a substituent, and the aliphatic heterocyclic group which may have a substituent are the same as those represented by the following formula:

[0037] Ring C Ｘ may be either a monocyclic or polycyclic ring. Ｘ When the aromatic ring is polycyclic, it preferably has a two- or three-fused ring structure in which a ring having >C=X therein is fused with one or two aromatic rings. The number of ring-membering atoms in the aromatic ring is preferably 5 to 10, more preferably 5 or 6. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of heteroatoms in the aromatic heterocycle include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen being preferred. The aromatic ring is preferably a benzene ring, naphthalene ring, thiophene ring, furan ring, thiazole ring, oxazole ring, imidazole ring, benzofuran ring, benzothiophene ring, thienothiophene ring, pyridine ring, or pyrimidine ring, more preferably a benzene ring or thiophene ring, and even more preferably a benzene ring. The aromatic ring may have a substituent. The number of substituents that the aromatic ring may have is preferably 1 to 6, and more preferably 1 to 3.

[0038] Ring C Ｘ The ring (having at least one >C=X within the ring) is preferably represented by any one of the following formulae (X-1) to (X-9).

[0039]

[0040] In formulas (X-1) to (X-7), each Y is independently —NR Ｃ１ -or-CRＣ２ ２ represents -, and R Ｃ１ and R Ｃ２ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent W, and among these, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, is preferred. Specific examples and preferred embodiments of the aliphatic hydrocarbon group which may have a substituent and the aromatic ring group which may have a substituent are R Ｑ１ In formulae (X-1) to (X-9), X each independently represents an oxygen atom, a sulfur atom, or ═NR Ｑ１ , or =CR Ｑ２ R Ｑ３ X is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. Ｑ１ ~R Ｑ３ The definition and preferred embodiments of are as described above. In formulae (X-2) to (X-9), Ar each independently represents an aromatic ring which may have a substituent. Specific examples and preferred embodiments of the aromatic ring which may have a substituent include ring C Ｘ Among these, the aromatic ring is preferably a benzene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, an imidazole ring, a benzofuran ring, a benzothiophene ring, a thienothiophene ring, a pyridine ring, or a pyrimidine ring, more preferably a benzene ring or a thiophene ring, and even more preferably a benzene ring.

[0041] Below, the above ring C Ａ (a ring having at least one acyl group) will be described in detail. Ａ Ring C may be either a monocyclic or polycyclic ring. It may be either an aromatic ring or a non-aromatic ring, but is preferably an aromatic ring. Ａ When Ring C is an aromatic ring, it may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Ａ The number of ring atoms in the ring C is preferably 5 to 10, and more preferably 5 or 6. ＡWhen ring C has a hetero atom, examples of the hetero atom 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 a sulfur atom, an oxygen atom, or a nitrogen atom is preferred. Ａ The ring structure therein is preferably a benzene ring, a naphthalene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, an imidazole ring, a benzofuran ring, a benzothiophene ring, a thienothiophene ring, a pyridine ring, or a pyrimidine ring, more preferably a benzene ring or a thiophene ring, and even more preferably a benzene ring.

[0042] Ring C Ａ The number of acyl groups contained in ring C is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Ａ However, when it has a substituent other than an acyl group, the number thereof is preferably 0 to 3, and more preferably 0 or 1. As the substituent other than an acyl group, a halogen atom such as a chlorine atom or a fluorine atom is preferred.

[0043] Ring C Ａ The acyl group in the formula is —(C═O)R Ａ is a group represented by R Ａ represents a hydrocarbon group. Ａ Examples of the hydrocarbon group represented by the formula include an aliphatic hydrocarbon group which may have a substituent and an aryl group which may have a substituent, and an aliphatic hydrocarbon group which may have a substituent is preferred.

[0044] Examples of the aliphatic hydrocarbon group in the optionally substituted aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 7, and even more preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic, with monocyclic being preferred. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 8, and even more preferably 3 to 6. The aryl group may be either monocyclic or polycyclic. The aryl group preferably has 5 to 15 ring atoms, more preferably 5 to 10, and even more preferably 5 to 6. The aryl group is preferably a phenyl group.

[0045] In formula (1-2), Ar ２ represents a ring having at least one structure selected from >C=X and -N= within the ring, or a ring having at least one substituent selected from an acyl group, a cyano group, and a halogen atom. ２ is preferably a ring having at least one >C=X in the ring or a ring having at least one acyl group.

[0046] Ar ２ When the ring represented by the formula (1-1) has >C=X in the ring, the number of >C=X is preferably 1 to 5, more preferably 1 or 2, and even more preferably 2. X has the same meaning as X in the formula (1-1) above, and the preferred embodiments thereof are also the same.

[0047] Ar ２ When the ring represented by the formula (I) has -N= in the ring, "having -N= in the ring" means that any of the ring atoms is a nitrogen atom, and the nitrogen atom forms a single bond and a double bond with the adjacent ring atom. ２When a ring represented by the formula (I) has -N= within the ring, the number of -N= is preferably 1 or 2, and more preferably 1. The ring having -N= within the ring may be either a monocyclic or polycyclic ring. Furthermore, it may be either an aromatic or non-aromatic ring, but an aromatic ring is preferred. The number of ring atoms of the ring having -N= within the ring is preferably 5 to 10, and more preferably 5 or 6. When the ring having -N= within the ring has a heteroatom other than a nitrogen atom, examples of the heteroatom include a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom or an oxygen atom being preferred. The ring having -N= within the ring may have a substituent. The number of substituents that the aromatic ring may have is preferably 1 to 6, and more preferably 1 to 3. Examples of the substituent include the groups exemplified for the substituent W above. Specific examples of the ring having -N= within the ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a triazole ring, a thiadiazole ring, a quinoline ring, a quinoxaline ring, a quinazoline ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, and a benzothiadiazole ring.

[0048] The ring having at least one substituent selected from the group consisting of an acyl group, a cyano group, and a halogen atom will be described in detail below. The ring may be either a monocyclic or polycyclic ring. It may be either an aromatic or non-aromatic ring, with an aromatic ring being preferred. When the ring is an aromatic ring, it may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of ring atoms in the ring is preferably 5 to 10, more preferably 5 or 6. When the ring has a heteroatom, examples of the heteroatom 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. The ring structure is preferably a benzene ring, a naphthalene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, an imidazole ring, a benzofuran ring, a benzothiophene ring, a thienothiophene ring, a pyridine ring, or a pyrimidine ring, more preferably a benzene ring or a thiophene ring, and even more preferably a benzene ring.

[0049] Regarding the ring having at least one substituent selected from an acyl group, a cyano group, and a halogen atom, specific examples and preferred embodiments of the acyl group include ring C Ａ The halogen atom is preferably a fluorine atom or a chlorine atom.

[0050] In the above formula (1-1) and the above formula (1-2), X １ and X ３ One of them is -NR Ｎ -, and the other represents a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ - represents. Ｎ each independently represents a hydrogen atom or a substituent. １ and X ３ As for one, -NR Ｎ - and the other is a sulfur atom or an oxygen atom. Ｎ As the substituent, for example, the groups exemplified as the substituent W above can be mentioned, and among them, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, is preferred. Specific examples and preferred embodiments of the aliphatic hydrocarbon group which may have a substituent and the aromatic ring group which may have a substituent are R Ｑ１ The aliphatic hydrocarbon group which may have a substituent and the aromatic ring group which may have a substituent are the same as those represented by the following formula:

[0051] In the above formula (1-1) and the above formula (1-2), X ２ and X ４ are each independently -CR Ｃ = or represents a nitrogen atom. Ｃ R each independently represents a hydrogen atom or a substituent. Ｃ is preferably a hydrogen atom. ２ and X ４ Each of the groups independently represents -CR Ｃ It is preferred that R represents ≡ Ｃ Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W above.

[0052] In the above formula (1-1) and the above formula (1-2), R１ represents a hydrogen atom or a substituent. １ A is preferably a hydrogen atom. A represents a group represented by formula (A-1) or a group represented by formula (A-2).

[0053]

[0054] In formula (A-1), C １ represents a ring containing two or more carbon atoms and 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.

[0055] Examples of the substituent that the ring may have include the groups exemplified by the substituent W. The ring may also 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, with a sulfur atom, a nitrogen atom, or an oxygen atom being preferred. The number of heteroatoms in the ring is preferably 0 to 10, and more preferably 0 to 5. The C １ Among the carbon atoms constituting the ring represented by the formula (A-1), the carbon atom at the bonding position marked with * and Y １ The carbon atom other than the carbon atom bonded to may be a carbonyl carbon or a thiocarbonyl carbon. Note that a "carbonyl carbon" refers to a carbon atom in a carbonyl group (-C=O), and a "thiocarbonyl carbon" refers to a carbon atom in a thiocarbonyl group (-C=S).

[0056] In the above formula (A-1), Y １ represents an oxygen atom, a sulfur atom, and ═NR Ｙ１, or =CR Ｙ２ R Ｙ３ Represents Y. １ is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom, in that the effects of the present invention are more excellent. Ｙ１ represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified above for the substituent W. Ｙ２ and R Ｙ３ each independently represents a cyano group, —SO ２ R Ｙ４ , -COOR Ｙ５ , or -COR Ｙ６ Represents R Ｙ４ ~R Ｙ６ R each independently represent 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. The definition of the aliphatic hydrocarbon group is as described above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The definition of the aromatic ring group is as described above, and an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. The definition of the aliphatic heterocyclic group is as described above, and the heteroatom contained in the aliphatic heterocyclic group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. R Ｙ４ ~R Ｙ６ Examples of the substituent that each group represented by the following formula may have include the substituents exemplified for the substituent W above.

[0057] 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, etc. (o) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione, etc. (p) Benzothiophen-3(2H)-one nucleus: for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one, etc. (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, etc. (r) Benzofuran-3-(2H)-one nucleus: for example, benzofuran-3-(2H)-one, etc. (s) 2,2-dihydrophenalene-1,3-dione nucleus, etc.

[0058] In the above formula (A-2), R Ａ１ and R Ａ２ each independently represents a cyano group, —SO ２ R Ｘ１ , -COOR Ｘ２ , or -COR Ｘ３ Represents R Ｘ１ ~R Ｘ３ 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. Ａ１ and R Ａ２ are each independently a cyano group or —COR Ｘ３ is preferred. Ｘ１~R Ｘ３ The definitions and preferred embodiments of each group represented by R Ｙ４ ~R Ｙ６ Among these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a phenyl group is preferred.

[0059] In the above formula (1-1) and formula (1-2), A is preferably a group represented by the above formula (A-1), more preferably a group represented by the following formula (A-3), and further preferably a group represented by the below-mentioned formula (C-1) or formula (C-2).

[0060]

[0061] In formula (A-3), C ２ represents a ring containing 3 or more carbon atoms and which may have a substituent. ２ The three carbon atoms contained in the ring are the three carbon atoms specified in formula (A-3). 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 contain 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. Above C ２ Among the carbon atoms constituting the ring represented by the formula (A-3), the carbon atom at the bonding position marked with * and W ２ Or W ３ The carbon atom other than the carbon atom bonded to may be a carbonyl carbon or a thiocarbonyl carbon. １ The substituents are the same as those that may be possessed by the group.

[0062] In formula (A-3), W ２ and W ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｙ１ , or =CR Ｙ２ R Ｙ３ Represents R Ｙ１ ~R Ｙ３ represents R in formula (A-1). Ｙ１ ~R Ｙ３ The preferred embodiments are also the same as those of the above. ２ and W ３ are each independently preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.

[0063] As described above, A is preferably a group represented by formula (C-1) or a group represented by formula (C-2), in terms of achieving better effects of the present invention.

[0064]

[0065] In formula (C-1), X ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｃ１ or =CR Ｃ２ R Ｃ３ The effect of the present invention is more excellent, and therefore, X ｃ１ and X ｃ２ Preferably, at least one of X is an oxygen atom, ｃ１ and X ｃ２ It is more preferable that R is an oxygen atom. Ｃ１ represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified above for the substituent W. Ｃ２ and R Ｃ３ each independently represents a cyano group, —SO ２ R Ｃ４ , -COOR Ｃ５ , or -COR Ｃ６ Represents R Ｃ４ ~R Ｃ６ 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. Ｃ４ ~RＣ６ The definitions and preferred embodiments of each group represented by R Ｙ４ ~R Ｙ６ Among these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a phenyl group is preferred.

[0066] In formula (C-1), C ３ represents an aromatic ring which may have a substituent. The aromatic ring may be either a monocyclic or polycyclic ring, but a monocyclic ring is preferred. 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 an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred. C ３ The aromatic ring represented by the formula (I) 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, a thienothiophene ring, or a pyridazine ring, more preferably a benzene ring, a naphthalene ring, or a thiophene ring, and even more 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.

[0067] In the above formula (C-2), X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｃ１ or =CR Ｃ２ R Ｃ３ The effect of the present invention is more excellent, and therefore, X ｃ３ and X ｃ４ is preferably an oxygen atom, and X ｃ３ ~X ｃ５ It is more preferable that R is an oxygen atom. Ｃ１ ~R Ｃ３ The definition and preferred embodiments of are as described above.

[0068] In the above formula (C-2), Z ｃ１ and Zｃ２ are each independently -NR Ｃ７ -or-CR Ｃ８ ２ represents -, and R Ｃ７ and R Ｃ８ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified by 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 or 2. The aryl group may be monocyclic or polycyclic, with a phenyl group being preferred. The aryl group may further have a substituent, and examples of the substituent include the groups exemplified by the substituent W above.

[0069] Specific examples of partial structures in specific compounds (compounds represented by formula (1-1) or formula (1-2)) are shown below, but the present invention is not limited to these. In each structural formula, * represents a bonding position. Specific examples of partial structures of the above formula (1-1), represented by the following formula (1-1-D), are shown below.

[0070]

[0071] Specific examples of the partial structure of the above formula (1-2), represented by the following formula (1-2-D), are shown below.

[0072]

[0073] Hereinafter, Ar in the above formula (1-1) １ or Ar in the above formula (1-2) ２ Specific examples of the ring represented by the following formula are shown below.

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] Specific examples of the structure represented by the above formula (A-1) are shown below.

[0082]

[0083]

[0084]

[0085] Specific examples of the structure represented by the above formula (A-2) are shown below.

[0086]

[0087] The molecular weight of the specific compound is preferably 300 to 1200, more preferably 350 to 1000, and even more preferably 400 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.

[0088] The specific compound preferably has an ionization potential of −5.0 to −6.5 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.

[0089] The maximum absorption wavelength of the specific compound is preferably in the wavelength range of 400 to 600 nm, more preferably in the range of 450 to 600 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 maximum absorption wavelength of the specific compound is determined by evaporating the specific compound and measuring the value using the specific compound in a film state.

[0090] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, an optical sensor, 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.

[0091] 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, and purification using an adsorbent such as activated carbon and recrystallization purification.

[0092] 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 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 20 to 50% 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.

[0093] <n-Type Organic Semiconductor> The photoelectric conversion film preferably further 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; fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); and 5- to 7-membered heterocyclic compounds having at least one atom 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, pyrazole, imidazole, and thiazole). polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic acid anhydride; 1,4,5,8-naphthalenetetracarboxylic acid diimide 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; 3,4,9,10-perylenetetracarboxylic acid dianhydride; 3,4,9,10-perylenetetracarboxylic acid diimide derivatives; and the compounds described in paragraphs

[0056] to

[0057] of JP-A No. 2006-100767.

[0094] 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.

[0095] The n-type organic semiconductor may be 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, acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0096] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0097] The maximum absorption wavelength of the n-type organic semiconductor is preferably in the range of 400 nm to 600 nm.

[0098] The photoelectric conversion film preferably has a bulk heterostructure formed by mixing a specific compound and an n-type organic semiconductor. The bulk heterostructure is a layer in the photoelectric conversion film in which the specific compound and the 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.

[0099] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0100] 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%.

[0101] 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.

[0102] 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 15 to 75% by volume, more preferably 30 to 75% 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.

[0103] <p-Type Organic Semiconductor> The photoelectric conversion film preferably further 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.

[0104] Examples of p-type organic semiconductors include triarylamine compounds (e.g., N,N'-diphenyl-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, 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][1]benzothiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzthiophene 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, compounds described in paragraph [004 5] 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 JP2019-080052A, 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 described in paragraphs

[0033] to

[0036] of JP-A No. 2018-206878, the compounds described in paragraph

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

[0019] to

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

[0031] to

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

[0036] to

[0041] of JP-A No. 2018-16620 Compounds described in paragraphs

[0055] to

[0082] of JP-A No. 2018-113425, compounds described in paragraphs

[0041] to

[0050] of JP-A No. 2018-113425, compounds described in paragraphs

[0044] to

[0048] of JP-A No. 2018-085430, compounds described in paragraphs

[0041] to

[0045] of JP-A No. 2018-056546, compounds described in paragraphs

[0042] to

[0049] of JP-A No. 2018-046267, compounds described in paragraphs

[0043] to

[0044] of JP-A No. 2018-014474 Compounds described in paragraphs

[0031] to

[0036] of WO2018 / 016465, compounds described in paragraphs

[0036] to

[0046] of JP2020-016465A, compounds described in paragraphs

[0045] to

[0048] of JP2020-010024A, 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. Examples of p-type organic semiconductors include benzoxazole compounds (for example, compounds described in Figures 3 to 7 of JP-A No. 2022-123944), dicarbazole compounds (for example, compounds described in Figures 2 to 5 of JP-A No. 2022-122839), benzoquinazoline compounds (for example, compounds described in paragraphs

[0053] to

[0056] of JP-A No. 2022-120323), and azine compounds (for example,compounds described in paragraphs

[0041] to

[0042] of JP-A No. 2022-120273), compounds described in Figures 2 to 10 of JP-A No. 2022-115832, indolotriphenylene compounds (for example, compounds described in paragraphs

[0065] to

[0072] of JP-A No. 2022-108268), indolocarbazole compounds (for example, compounds described in paragraphs

[0052] to

[0073] of JP-A No. 2023-005703, Examples of p-type organic semiconductors include compounds having a lower 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 semiconductors include: triscarbazolylphenyl compounds (for example, compounds described in paragraphs

[0038] to

[0040] of JP-A No. 2022-181226); compounds described in paragraphs

[0070] to

[0082] of JP-A No. 2022-027575; and compounds described in paragraphs

[0051] to

[0064] of JP-A No. 2021-163968. Examples of p-type organic semiconductors include compounds having a lower 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 semiconductors are listed below.

[0105]

[0106]

[0107]

[0108]

[0109] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0110] 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%.

[0111] 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.

[0112] <Dye> The photoelectric conversion film may further contain 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, Examples of the organic dye include acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes and metal complex dyes, imidazoquinoxaline dyes described in WO 2020 / 013246, WO 2022 / 168856, JP 2023-10305 A, and JP 2023-10299 A, 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, cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred as organic dyes, as they have a maximum absorption wavelength in the preferred range described below.

[0113] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably from 400 to 700 nm, and even more preferably from 400 to 650 nm.

[0114] The content of the dye in the photoelectric conversion film relative to the total content of the specific compound and the dye (=(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 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.

[0115] In addition to the components described above, the photoelectric conversion film may further contain optional components. Examples of optional components include antioxidants, dispersants, and ultraviolet absorbers. The optional components may also be impurities derived from specific compounds, n-type organic semiconductors, p-type organic semiconductors, or dyes. When the photoelectric conversion film contains optional components, the content of the optional components in the photoelectric conversion film (film thickness of the optional components in terms of a single layer / film thickness of the photoelectric conversion film × 100) is preferably 0.01 to 10% by volume, and more preferably 0.01 to 1% by volume.

[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, copper, chromium, aluminum, 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), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine, etc.; metals such as gold, silver, copper, 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] [Method for manufacturing photoelectric conversion element] Examples of methods for manufacturing photoelectric conversion elements include known manufacturing methods. Specifically, for example, a method for manufacturing a photoelectric conversion element includes a step of forming a conductive film on a substrate, a step of forming a photoelectric conversion film, and a step of forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer) in addition to the above. The method for forming each layer is as described above.

[0131] [Imaging element] An example of an application of a photoelectric conversion element is an imaging element. An imaging 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 imaging element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The manufacturing method of an imaging element is not particularly limited, but examples include a method including the step of manufacturing the photoelectric conversion element described above.

[0132] [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.

[0133] [Compound] The present invention also includes the invention of a compound. The compound of the present invention is the above-mentioned specific compound.

[0134] The present invention will be described in more detail below with reference to the following 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 following examples.

[0135] [Compounds used in photoelectric conversion film]

[0136] [Synthesis of Compound (B-1)] Compound (B-1) was synthesized according to the following scheme.

[0137]

[0138] <Synthesis of Compound (B-1a)> Compound (B-1a) was synthesized with reference to the method described in Non-Patent Document (Tetrahedron, 68 (2012), p. 9795.).

[0139] <Synthesis of Compound (B-1b)> 1.51 g of compound (B-1a) and 30 mL of chloroform were added to a flask, and while stirring at room temperature, 1.78 g of N-bromosuccinimide (NBS) was added, and the mixture was stirred at room temperature for 2 hours. 30 mL of aqueous sodium thiosulfate solution was added to the resulting reaction solution, and the organic layer obtained by separation was concentrated. Purification by silica gel column chromatography (developing solvent: hexane / ethyl acetate) yielded 1.14 g of compound (B-1b).

[0140] <Synthesis of Compound (B-1c)> 1.10 g of compound (B-1b), 1.38 g of potassium carbonate, and 20 mL of N,N-dimethylformamide (DMF) were added to a flask, and while stirring at room temperature, 0.80 g of ethyl iodide was added, followed by stirring at room temperature for 18 hours. 30 mL of an aqueous ammonium chloride solution and 30 mL of ethyl acetate were added to the resulting reaction solution, and the organic layer obtained by separation was concentrated. Purification by silica gel column chromatography (developing solvent: hexane / ethyl acetate) yielded 1.18 g of compound (B-1c).

[0141] <Synthesis of Compound (B-1d)> In a flask under a nitrogen atmosphere, 1.00 g of compound (B-1c), 2.30 g of hexabutylditin, and 20 mL of toluene were added, and while stirring at room temperature, 0.30 g of SPhos Pd G3 was added, and the mixture was stirred at 70°C for 2 hours. The resulting reaction solution was filtered through Celite, and the filtrate was concentrated. The mixture was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate), to obtain 1.45 g of compound (B-1d).

[0142] <Synthesis of Compound (B-1e)> In a flask under a nitrogen atmosphere, 1.45 g of compound (B-1d), 0.82 g of 4-bromo-N-methylphthalimide, and 30 mL of DMF were added, and while stirring at room temperature, 0.36 g of tetrakis(triphenylphosphine)palladium was added, followed by stirring at 100°C for 3 hours. 30 mL of an aqueous ammonium chloride solution was added to the resulting reaction solution, and the precipitate was collected by filtration. The mixture was purified by silica gel column chromatography (developing solvent: chloroform / ethyl acetate), yielding 0.63 g of compound (B-1e).

[0143] <Synthesis of Compound (B-1)> 0.214 g of compound (B-1e), 0.20 g of dimethylbarbituric acid, and 20 mL of toluene were added to a 100 mL flask, and while stirring at room temperature, 0.015 g of piperidine was added, followed by stirring at 70°C for 2 hours. 40 mL of methanol was added to the reaction solution, and the precipitate was collected by filtration. 0.35 g of compound (B-1) was obtained by crystallization purification using chloroform / methanol. The structure of compound B-1 was confirmed by LDI-MS (laser desorption ionization mass spectrometry). LDI-MS (compound B-1): 477 (M+H ＋ )

[0144] The compounds used in the photoelectric conversion film of each of the Examples and Comparative Examples other than the compound (B-1) were synthesized according to the synthesis method of the compound (B-1).

[0145] The materials used in the preparation of the photoelectric conversion film are shown below. The comparative compounds shown below are compounds used in place of specific compounds in the comparative examples.

[0146] [Specific compound]

[0147]

[0148]

[0149] [Comparative Compounds]

[0150]

[0151] [n-type organic semiconductor] Fullerene (C ６０ )

[0152] [p-type organic semiconductor]

[0153]

[0154] [Evaluation] The quantum efficiency, electric field strength dependence of quantum efficiency, response speed, electric field strength dependence of response speed, and manufacturability when the photoelectric conversion element received green and red light were evaluated by the following methods.

[0155] <Preparation of Photoelectric Conversion Element> A photoelectric conversion element having the configuration shown in FIG. 2 was prepared using the various components shown above. 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). Subsequently, with the glass substrate at room temperature, each specific compound or each comparative compound shown in Table 1 and an n-type organic semiconductor (fullerene (C ６０ )) and a p-type organic semiconductor shown in Table 1 were co-deposited by vacuum deposition to form a film having a thickness of 80 nm in terms of a single layer. This resulted in a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. At this time, the film formation rate of the photoelectric conversion film 12 was 1.0 Å / sec. Furthermore, a 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). After a SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al ２ O ３ The resulting laminate was heated in a glove box at 150° C. for 30 minutes to obtain a photoelectric conversion element.

[0156]

[0157] <Dark Current> The dark current of each of the obtained photoelectric conversion elements was measured by the following method. ５ A voltage was applied to the photoelectric conversion element so as to obtain an electric field strength of 50 nA / cm. The current value in a dark place (dark current) was measured. As a result, the dark current was 50 nA / cm for all the photoelectric conversion elements. ２ It was confirmed that the dark current was sufficiently low.

[0158] <Quantum Efficiency> The quantum efficiency of each photoelectric conversion element was measured by the following method. ５ After applying a voltage to achieve an electric field strength of 1000 V / cm, light was irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 560 nm, and the quantum efficiency (relative ratio) was calculated according to formula (S1). From the obtained value, the quantum efficiency was evaluated according to the following evaluation criteria. The quantum efficiency is preferably rated C or higher. Formula (S1): Quantum efficiency (relative ratio) = (photoelectric conversion efficiency of each photoelectric conversion element) / (photoelectric conversion efficiency of the photoelectric conversion elements of Examples 1-23)

[0159] (Evaluation criteria) A: Quantum efficiency (relative ratio) is 1.4 or more B: Quantum efficiency (relative ratio) is 1.2 or more and less than 1.4 C: Quantum efficiency (relative ratio) is 0.8 or more and less than 1.2 D: Quantum efficiency (relative ratio) is less than 0.8

[0160] <Dependence of Quantum Efficiency on Electric Field Strength> The dependence of quantum efficiency on electric field strength was evaluated for each photoelectric conversion element by the following method. In the evaluation of the above <Quantum Efficiency>, a voltage of 7.5×10 ４ The same procedure was followed except that the pressure was changed to 7.5 × 10 ４ The quantum efficiency (photoelectric conversion efficiency) at a wavelength of 560 nm was measured. The electric field strength dependency of the quantum efficiency was calculated according to formula (S2), and the electric field strength dependency of the quantum efficiency was evaluated according to the following evaluation criteria. In formula (S2), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same example or comparative example. For example, with respect to Example 1-1, the photoelectric conversion efficiency of Example 1-1 was 7.5 × 10 at a wavelength of 560 nm. ４ V / cm and the photoelectric conversion efficiency of Example 1-1 at a wavelength of 560 nm of 2.0 × 10 ５ The quantum efficiency at 7.5 × 10 V / cm is compared with the quantum efficiency at 7.5 × 10 V / cm. ４ V / cm) / (electric field strength of each photoelectric conversion element 2.0×10 ５ Quantum efficiency in V / cm

[0161] (Evaluation Criteria) A: The electric field strength dependency of quantum efficiency is 0.9 or more. B: The electric field strength dependency of quantum efficiency is 0.8 or more and less than 0.9. C: The electric field strength dependency of quantum efficiency is 0.7 or more and less than 0.8. D: The electric field strength dependency of quantum efficiency is less than 0.7.

[0162] <Response Speed ​​(Responsivity)> The response speed of each photoelectric conversion element was evaluated by the following method. ５ A voltage was applied so that the intensity was 1000 V / cm. Thereafter, an 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 560 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity, and the relative response speed was calculated according to formula (S3). From the obtained value, the response speed was evaluated according to the following evaluation criteria. Formula (S3): Relative response speed = (rise time of each photoelectric conversion element at a wavelength of 460 nm) / (rise time of the photoelectric conversion element of Example 1-23 at a wavelength of 460 nm)

[0163] (Evaluation Criteria) 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

[0164] <Dependence of response speed on electric field strength> The dependence of response speed on electric field strength of each photoelectric conversion element was evaluated by the following method. In the evaluation of the above <Response speed>, a voltage of 7.5×10 ４ The same procedure was followed except that the voltage was changed to 7.5 × 10 ４ The response speed at 7.5 V / cm was measured. The electric field strength dependency of the response speed was calculated according to formula (S4), and the electric field strength dependency of the response speed was evaluated according to the following evaluation criteria. The electric field strength dependency of the response speed is preferably rated B or higher. In formula (S4), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. Formula (S4): Electric field strength dependency of response speed = (electric field strength of each photoelectric conversion element 7.5 × 10 ４V / cm) / (electric field strength of each photoelectric conversion element 2.0×10 ５ rise time in V / cm)

[0165] (Evaluation Criteria) A: The electric field strength dependency of the response speed is less than 2.0 B: The electric field strength dependency of the response speed is 2.0 or more and less than 3.0 C: The electric field strength dependency of the response speed is 3.0 or more and less than 4.0 D: The electric field strength dependency of the response speed is 4.0 or more

[0166] <Manufacturing Suitability> The manufacturability of each photoelectric conversion element was evaluated using the following method. Each photoelectric conversion element (B) was produced using the same procedure as in the above <Preparation of Photoelectric Conversion Element>, except that the deposition rate of the photoelectric conversion film 12 was 3.0 Å / sec. The quantum efficiency (photoelectric conversion efficiency) of the obtained photoelectric conversion element (B) was measured using the same method as in the above <Quantum Efficiency>. The photoelectric conversion element obtained in the above <Preparation of Photoelectric Conversion Element>, in which the deposition rate of the photoelectric conversion film 12 was 1.0 Å / sec, was designated as photoelectric conversion element (A), and the relative ratio B / A of quantum efficiency (photoelectric conversion efficiency) was calculated according to formula (S5). From the obtained value, the manufacturability was evaluated according to the following evaluation criteria. In formula (S5), the photoelectric conversion element (B) and the photoelectric conversion element (A) in the numerator and denominator are photoelectric conversion elements produced using the same material. The closer the value of the relative ratio B / A is to 1, the less the performance of the photoelectric conversion element is likely to deteriorate even when the film formation rate is increased, i.e., the more excellent the manufacturability. Formula (S5): Relative ratio B / A=(Photoelectric conversion efficiency of photoelectric conversion element (B)) / (Photoelectric conversion efficiency of photoelectric conversion element (A)).

[0167] (Evaluation Criteria) 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 less than 0.80.

[0168] [Results] The evaluation results are shown in Table 1 below. In the table, in Examples 1-14 to 1-20, the compound represented by formula (1-2) was used as the specific compound, and in the other Examples, the compound represented by formula (1-1) was used as the specific compound. In the table, the "Ar" column indicates the specific compound used, １ or Ar２ The descriptions ">C=X", "acyl", "-N=", "cyano" and "halogen" indicate that the ring has either >C=X, an acyl group, -N=, a cyano group or a halogen atom, respectively. １ = Ar ２ " column indicates the presence of Ar in a specific compound. １ or Ar ２ is a ring having at least one >C=X in the ring or a ring having at least one acyl group, the group is designated as "A", and other cases are designated as "B". Ｃ The "=" column indicates that a specific compound has X ２ and X ４ are each independently -CR Ｃ = was recorded as "A", and in other cases, it was recorded as "B". In the table, in the "Formula (1-1)" column, if the specific compound is a compound represented by the above formula (1-1), it was recorded as "A", and in other cases, it was recorded as "B". In the table, in the "Formula (A-1)" column, if A in the specific compound is a group represented by the above formula (A-1), it was recorded as "A", and in other cases, it was recorded as "B". In the table, in the "Formula (A-3)" column, if A in the specific compound is a group represented by the above formula (A-3), it was recorded as "A", and in other cases, it was recorded as "B". In the table, in the "Formula (C-1) or Formula (C-2)" column, if A in the specific compound is a group represented by formula (C-1) or a group represented by formula (C-2), it was recorded as "A", and in other cases, it was recorded as "B".

[0169]

[0170] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention has excellent quantum efficiency when receiving green and red light, and that the response speed (responsivity) has little dependence on electric field strength. １ or Ar ２ It was confirmed that when the ring has at least one >C=X in the ring or a ring having at least one acyl group, the electric field strength dependency of the quantum efficiency is more excellent. ２and X ４ are each independently -CR Ｃ =, it was confirmed that the electric field strength dependence of the quantum efficiency was better. From a comparison between Examples 1-1 to 1-6 and Example 1-14, it was confirmed that when the specific compound was a compound represented by the above formula (1-1), the quantum efficiency was better. From a comparison between Example 1-22 and Example 1-23, it was confirmed that when A in the specific compound was a group represented by the above formula (A-1), the quantum efficiency and response speed were better. From a comparison between Example 1-21 and Example 1-22, it was confirmed that when A in the specific compound was a group represented by the above formula (A-3), the electric field strength dependence of the response speed was better. From a comparison between Examples 1-1 to 1-6 and Example 1-21, it was confirmed that when A in the specific compound was a group represented by formula (C-1) or a group represented by formula (C-2), at least one effect of quantum efficiency, response speed, electric field strength dependence of quantum efficiency, and manufacturability was better.

[0171] 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, wherein the photoelectric conversion film contains a compound represented by formula (1-1) or formula (1-2). In formula (1-1), Ar １ represents a ring having at least one >C=X in the ring, or a ring having at least one acyl group. X represents an oxygen atom, a sulfur atom, =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ represents. R Ｑ１ represents a hydrogen atom or a substituent. R Ｑ２ and R Ｑ３ each independently represent a cyano group, -SO ２ R Ｑ４ , -COOR Ｑ５ , or -COR Ｑ６ represents. R Ｑ４ to R Ｑ６ each independently represent an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. In formula (1-2), Ar ２ represents a ring having at least one structure selected from >C=X and -N= in the ring, or a ring having at least one substituent selected from an acyl group, a cyano group, and a halogen atom. X has the same meaning as X in formula (1-1). In formula (1-1) and formula (1-2), １ one of X ３ and X Ｎ represents -NR Ｎ -, and the other represents a sulfur atom, an oxygen atom, a selenium atom, or -NR ２ and X ４ each independently represent -CR Ｃ = or a nitrogen atom. R Ｎ and R Ｃ each independently represent a hydrogen atom or a substituent. When there are a plurality of R Ｎ , the plurality of R Ｎ may be the same or different from each other. When there are a plurality of R Ｃ , the plurality of R Ｃ may be the same or different from each other. R １ represents a hydrogen atom or a substituent. A represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (A-1), C １ represents a ring containing 2 or more carbon atoms and may have a substituent. Y １ represents an oxygen atom, a sulfur atom, =NR Ｙ１ or =CR Ｙ２ R Ｙ３ represents a hydrogen atom or a substituent. R Ｙ１ represents a hydrogen atom or a substituent. R Ｙ２ and R Ｙ３ each independently represent a cyano group, -SO ２ R Ｙ４ -COOR Ｙ５ or -COR Ｙ６ represents a hydrogen atom or a substituent. R Ｙ４ to R Ｙ６ each independently represent 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. In formula (A-2), R Ａ１ and R Ａ２ each independently represent a cyano group, -SO ２ R Ｘ１ -COOR Ｘ２ or -COR Ｘ３ represents a hydrogen atom or a substituent. R Ｘ１ to R Ｘ３ each independently represent 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. * represents the bonding position.

2. Ar ２ The photoelectric conversion element according to claim 1, wherein Ar is a ring having at least one >C=X in the ring or a ring having at least one acyl group.

3. In the formula (1-1) and the formula (1-2), X ２ and X ４ each independently represents -CR Ｃ =, The photoelectric conversion element according to claim 1.

4. The photoelectric conversion device according to claim 1, wherein the compound is a compound represented by the formula (1-1).

5. The photoelectric conversion device according to claim 1, wherein A is a group represented by the formula (A-1).

6. The photoelectric conversion element according to claim 1, wherein A is a group represented by the formula (A-3). In the formula (A-3), C ２ represents a ring containing 3 or more carbon atoms and may have a substituent. W ２ and W ３ each independently represents an oxygen atom, a sulfur atom, =NR Ｙ１ , or =CR Ｙ２ R Ｙ３ represents. R Ｙ１ to R Ｙ３ are synonymous with R Ｙ１ to R Ｙ３ in the formula (A-1). * represents the bonding position.

7. The photoelectric conversion element according to any one of claims 1 to 6, wherein A is a group represented by formula (C-1) or formula (C-2). In formula (C-1), X ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, =NR Ｃ１ or =CR Ｃ２ R Ｃ３ represents. R Ｃ１ represents a hydrogen atom or a substituent. R Ｃ２ and R Ｃ３ each independently represents a cyano group, -SO ２ R Ｃ４ -COOR Ｃ５ or -COR Ｃ６ represents. R Ｃ４ to R Ｃ６ each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. C ３ represents an optionally substituted aromatic ring. In formula (C-2), X ｃ３ to X ｃ５ each independently represents an oxygen atom, a sulfur atom, =NR Ｃ１ or =CR Ｃ２ R Ｃ３ represents. R Ｃ１ represents a hydrogen atom or a substituent. R Ｃ２ and R Ｃ３ each independently represents a cyano group, -SO ２ R Ｃ４ -COOR Ｃ５ or -COR Ｃ６ represents. R Ｃ４ to R Ｃ６ each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. Z ｃ１ and Z ｃ２ each independently represents -NR Ｃ７ - or -CR Ｃ８ ２ - represents, and R Ｃ７ and R Ｃ８ each independently represents a hydrogen atom or a substituent. * represents the bonding position.

8. The photoelectric conversion device according to any one of claims 1 to 6, wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterojunction structure formed in a state where the compound and the n-type organic semiconductor are mixed.

9. The photoelectric conversion device according to claim 8, wherein the n-type organic semiconductor contains fullerenes selected from the group consisting of fullerene and its derivatives.

10. The photoelectric conversion device according to any one of claims 1 to 6, wherein the photoelectric conversion film further contains a p-type organic semiconductor.

11. The photoelectric conversion device according to any one of claims 1 to 6, wherein the photoelectric conversion film further contains a dye.

12. The photoelectric conversion device according to any one of claims 1 to 6, having 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 having the photoelectric conversion device according to any one of claims 1 to 6.

14. An optical sensor having the photoelectric conversion device according to any one of claims 1 to 6.

15. A method for manufacturing an imaging device, having a step of manufacturing the photoelectric conversion device according to any one of claims 1 to 6.

16. A compound represented by formula (1-1) or formula (1-2). In formula (1-1), Ar １ represents a ring having at least one >C=X in the ring, or a ring having at least one acyl group. X represents an oxygen atom, a sulfur atom, =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ represents. R Ｑ１ represents a hydrogen atom or a substituent. R Ｑ２ and R Ｑ３ each independently represent a cyano group, -SO ２ R Ｑ４ , -COOR Ｑ５ , or -COR Ｑ６ represents. R Ｑ４ to R Ｑ６ each independently represent an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. In formula (1-2), Ar ２ represents a ring having at least one structure selected from >C=X and -N= in the ring, or a ring having at least one substituent selected from an acyl group, a cyano group, and a halogen atom. X has the same meaning as X in formula (1-1). In formula (1-1) and formula (1-2), one of X １ and X ３ represents -NR Ｎ -, and the other represents a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ -. X ２ and X ４ each independently represent -CR Ｃ = or a nitrogen atom. R Ｎ and R Ｃ each independently represent a hydrogen atom or a substituent. When there are a plurality of R Ｎ , the plurality of R Ｎ may be the same or different from each other. When there are a plurality of R Ｃ , the plurality of R Ｃ may be the same or different from each other. R １ represents a hydrogen atom or a substituent. A represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (A-1), C １ represents a ring containing 2 or more carbon atoms and may have a substituent. Y １ represents an oxygen atom, a sulfur atom, =NR Ｙ１ or =CR Ｙ２ R Ｙ３ represents. R Ｙ１ represents a hydrogen atom or a substituent. R Ｙ２ and R Ｙ３ each independently represent a cyano group, -SO ２ R Ｙ４ -COOR Ｙ５ or -COR Ｙ６ represents. R Ｙ４ to R Ｙ６ each independently represent 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. In formula (A-2), R Ａ１ and R Ａ２ each independently represent a cyano group, -SO ２ R Ｘ１ -COOR Ｘ２ or -COR Ｘ３ represents. R Ｘ１ to R Ｘ３ each independently represent 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. * represents the bonding position.

17. Ar ２ The compound according to claim 16, wherein Ar is a ring having at least one >C=X in the ring or a ring having at least one acyl group.

18. In the formula (1-1) and the formula (1-2), X ２ and X ４ each independently represents -CR Ｃ =, the compound according to claim 16.

19. The compound according to claim 16, wherein the compound is a compound represented by the formula (1-1).

20. The compound according to claim 16, wherein A is a group represented by the formula (A-1).

21. The compound according to claim 16, wherein A is a group represented by formula (A-3). In formula (A-3), C ２ represents a ring containing 3 or more carbon atoms and may have a substituent. W ２ and W ３ each independently represents an oxygen atom, a sulfur atom, =NR Ｙ１ , or =CR Ｙ２ R Ｙ３ represents. R Ｙ１ to R Ｙ３ are synonymous with R Ｙ１ to R Ｙ３ in the said formula (A-1). * represents a bonding position.

22. The compound according to any one of claims 16 to 21, wherein A is a group represented by formula (C-1) or formula (C-2). In formula (C-1), X ｃ１ and X ｃ２ are each independently an oxygen atom, a sulfur atom, =NR Ｃ１ or =CR Ｃ２ R Ｃ３ represents. R Ｃ１ represents a hydrogen atom or a substituent. R Ｃ２ and R Ｃ３ are each independently a cyano group, -SO ２ R Ｃ４ ,-COOR Ｃ５ or -COR Ｃ６ represents. R Ｃ４ to R Ｃ６ each independently represent an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. C ３ represents an optionally substituted aromatic ring. In formula (C-2), X ｃ３ to X ｃ５ are each independently an oxygen atom, a sulfur atom, =NR Ｃ１ or =CR Ｃ２ R Ｃ３ represents. R Ｃ１ represents a hydrogen atom or a substituent. R Ｃ２ and R Ｃ３ are each independently a cyano group, -SO ２ R Ｃ４ ,-COOR Ｃ５ or -COR Ｃ６ represents. R Ｃ４ to R Ｃ６ each independently represent an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. Z ｃ１ and Z ｃ２ are each independently -NR Ｃ７ - or -CR Ｃ８ ２ - represents, and R Ｃ７ and R Ｃ８ each independently represent a hydrogen atom or a substituent. * represents the bonding position.

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