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

Abstract

The present invention provides a photoelectric conversion element in which the dependence of quantum efficiency on electric field intensity is small with respect to red and green light. A photoelectric conversion element according to the present invention comprises a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film includes a prescribed compound.

Description

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

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

[0002] In recent years, development of devices having photoelectric conversion films (e.g., image sensors) has progressed. For example, Patent Document 1 discloses a compound having a specific structure as a compound that can be applied to organic semiconductor materials such as organic solar cells.

[0003] International Publication No. 2015 / 024848

[0004] 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. One of the characteristics required for a photoelectric conversion element is that the quantum efficiency of the photoelectric conversion element is unlikely to change even when the electric field strength is changed, that is, the quantum efficiency has a small electric field strength dependency. In response to this demand, the present inventors fabricated and investigated a photoelectric conversion element containing the compound disclosed in Patent Document 1, and found that the quantum efficiency for red and green light has a high electric field strength dependency, leaving room for improvement. In this specification, the red and green light refers to light with a wavelength of 500 to 700 nm.

[0005] Therefore, an object of the present invention is to provide a photoelectric conversion element having a quantum efficiency for red and green light that has a small electric field strength dependency. Another object of the present invention is to provide an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound related to the photoelectric conversion element.

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

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described below. [2] Y １ and Y ２ are each independently -CR Ｙ１ =, and Y ３ ~Y ２０ are each independently -CRＹ２ [3] The photoelectric conversion element according to [1], wherein X represents １ and X ２ One of them is -NR Ｚ１ The photoelectric conversion element according to [1] or [2], wherein Ar represents -, and the other represents a sulfur atom or an oxygen atom. １ [5] The photoelectric conversion element according to any one of [1] to [3], wherein R is a group represented by the above formula (Ar-1) or a group represented by the above formula (Ar-2). Ｚ１ is a group selected from the group consisting of a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent. [6] R Ｚ１ is a group selected from the group consisting of a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent. [7] A １ and A ２are each independently a group represented by formula (A-1) above. [8] The photoelectric conversion element according to any one of [1] to [7], wherein the groups represented by formula (A-1) are each independently a group represented by formula (C-1) or formula (C-2) described later. [9] The photoelectric conversion element according to any one of [1] to [8], wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) above with the n-type organic semiconductor.

[10] The photoelectric conversion element according to [9], wherein the n-type organic semiconductor contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.

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

[10] , wherein the photoelectric conversion film further contains a p-type organic semiconductor.

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

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

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

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

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

[13] .

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

[13] .

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

[13] .

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

[18] Y １ and Y ２ are each independently -CR Ｙ１ =, and Y ３ ~Y ２０ are each independently -CR Ｙ２

[19] The compound according to

[17] , wherein X represents １ and X ２ One of them is -NR Ｚ１ The compound according to

[17] or

[18] , wherein Ar represents - and the other represents a sulfur atom or an oxygen atom. １

[21] The compound according to any one of

[17] to

[19] , wherein R is a group represented by the above formula (Ar-1) or a group represented by the above formula (Ar-2).Ｚ１ is a group selected from the group consisting of a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent. Ｚ１ is a group selected from the group consisting of a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent.

[23] A １ and A ２ are each independently a group represented by the above formula (A-1).

[24] The compound according to any one of

[17] to

[23] , wherein the groups represented by the above formula (A-1) are each independently 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 a quantum efficiency for red and green light that has little dependence on electric field strength can be provided. Furthermore, according to the present invention, an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound related to the photoelectric conversion element can also 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] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

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

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

[0014] (Substituent W) The substituent W in this specification will be described. Examples of the substituent W include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (a 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 substituents 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. Each of the above groups may further have a substituent (e.g., one or more of the above groups) if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. When the substituent W has carbon atoms, the number of carbon atoms contained in the substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30. The specific compounds described below may have, as substituents, a carboxy group, a salt of a carboxy group, a phosphate group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) ２ ) and / or does not have a primary amino group.

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

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

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

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

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

[0020] In this specification, the term "aromatic ring group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic ring. In this specification, the term "aromatic hydrocarbon group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic hydrocarbon ring, and the term "aromatic heterocyclic group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic heterocycle. In this specification, the term "aryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to the aromatic hydrocarbon ring of the above-mentioned aromatic ring. In this specification, the term "heteroaryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to the aromatic heterocycle of the above-mentioned aromatic ring. In this specification, the term "arylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to the aromatic hydrocarbon ring of the above-mentioned aromatic ring. In this specification, the term "heteroarylene group" refers to, 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 aromatic ring group which may have a substituent, the aryl group which may have a substituent, the heteroaryl group which may have a substituent, the arylene group which may have a substituent, and the heteroarylene group which may have a substituent, the types of substituents which these groups may have include, for example, the groups exemplified for the substituent W. When these groups have a substituent, the number of the substituents may be 1 or more (for example, 1 to 4, etc.).

[0021] As used herein, the term "non-aromatic ring" refers to a ring structure that does not fall under the category of aromatic rings, and examples thereof include aliphatic hydrocarbon rings and aliphatic heterocycles. Examples of the aliphatic hydrocarbon ring include cycloalkanes, cycloalkenes, and cycloalkynes. Examples of the aliphatic heterocycle include a pyrrolidine ring, oxolane ring, thiolane ring, piperidine ring, tetrahydropyran ring, thiane ring, piperazine ring, morpholine ring, quinuclidine ring, azetidine ring, oxetane ring, aziridine ring, dioxane ring, and γ-butyrolactone ring. As used herein, the term "aliphatic hydrocarbon ring group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that falls under the category of an aliphatic hydrocarbon ring. As used herein, the term "aliphatic heterocyclic group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that falls under the category of an aliphatic heterocycle.

[0022] In this specification, when a formula representing a chemical structure contains a plurality of identical symbols representing the type or number of groups, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different, unless otherwise specified. In this specification, when a formula representing a chemical structure contains a plurality of groups of the same type (e.g., alkyl groups, etc.), the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the plurality of groups of the same type may be the same or different, unless otherwise specified.

[0023] In this specification, the bonding direction of a divalent group (e.g., -CO-O-, etc.) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be either "X-O-CO-Z" or "X-CO-O-Z."

[0024] 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.

[0025] In this specification, unless otherwise specified, * in a formula indicates a bonding position.

[0026] [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) (hereinafter also referred to as a "specific compound").

[0027] 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 ADA-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 when the electric field strength is low, and carriers can move efficiently, i.e., the electric field strength dependence of the quantum efficiency is thought to be small. Hereinafter, a smaller electric field strength dependence of the quantum efficiency is also referred to as "the effect of the present invention is better."

[0028] 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.

[0029] 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 ７ In 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.

[0030] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film.

[0031] <Specific Compound> The photoelectric conversion film contains a specific compound, which is a compound represented by formula (1).

[0032]

[0033] In formula (1), Y １ and Y ２ are each independently -CR Ｙ１ = or -N=. Ｙ１ represents a hydrogen atom or a substituent. １ and X ２ One of them is -NR Ｚ１ -, and the other represents a sulfur atom, an oxygen atom, or a selenium atom. Ｚ１ 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. １ represents a group represented by any one of formulas (Ar-1) to (Ar-5) described later. n represents 0 or 1. R １ and R ２ each independently represents a hydrogen atom or a substituent. １ and A ２ each independently represents a group represented by formula (A-1) described later or a group represented by formula (A-2) described later.

[0034] In the above formula (1), X １ and X ２ One of them is -NR Ｚ１ -, and the other represents a sulfur atom, an oxygen atom, or a selenium atom. １ and X ２ One of them is -NR Ｚ１ Preferably, one represents - and the other represents a sulfur atom or an oxygen atom.

[0035] R Ｚ１ 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. Examples of the substituent that each of the above-mentioned groups which may have a substituent include the substituents exemplified for the substituent W described above, and a substituent selected from the substituent group S described below is preferred.

[0036] R Ｚ１ The aliphatic hydrocarbon group represented by the formula (I) may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The linear aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 3, and particularly preferably 1 to 2. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 4. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 6.

[0037] R Ｚ１ The aromatic ring group represented by the formula (I) may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic ring group may be either a monocyclic or polycyclic ring, with a monocyclic group being preferred. The aromatic ring group preferably has 5 to 18 ring members, more preferably 5 to 10, and even more preferably 5 to 8. The aromatic ring group preferably has 4 to 18 carbon atoms, more preferably 4 to 10. The definition and specific examples of the aromatic hydrocarbon group are as described above, with a phenyl group or a naphthyl group being preferred, and a phenyl group being more preferred. 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. The definition and specific examples of the aromatic heterocyclic group are as described above, with a thiophene ring group, a furan ring group, or a selenophene ring group being preferred. The aromatic ring group may have a substituent, as described above. When the aromatic ring group has a substituent, the number of the substituents is not particularly limited, but 1 to 3 is preferred.

[0038] The definition of the aliphatic heterocyclic group is as described above. Ｚ１The number of ring members in the aliphatic heterocyclic group represented by the formula (I) 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.

[0039] The effect of the present invention is more excellent. Ｚ１ Among these, preferred is a group selected from the group consisting of a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent, and more preferred is a group selected from the group consisting of a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent.

[0040] Substituent group S will be described in detail. Substituent group S: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 7 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, aromatic ring groups having 3 to 20 ring members which may have a substituent, and halogen atoms.

[0041] The number of carbon atoms in the linear aliphatic hydrocarbon group in the above-mentioned substituent group S is 1 to 3, and more preferably 1 or 2. The number of carbon atoms in the branched aliphatic hydrocarbon group in the above-mentioned substituent group S is 3 to 7, and more preferably 3 or 4. The cyclic aliphatic hydrocarbon group in the above-mentioned substituent group S is preferably monocyclic.

[0042] The aromatic ring group in the substituent group S may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The heteroatom contained in the aromatic heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The number of ring members in the aromatic ring group is 3 to 20, preferably 5 to 12, and more preferably 5 or 6. Examples of the substituent that the aromatic ring group may have include the substituents exemplified for the substituent W above, with a substituent selected from the substituent group S being preferred, and a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 7 carbon atoms, or a halogen atom being more preferred. When the aromatic ring group has a substituent, the number of substituents is preferably 1 to 3.

[0043] Examples of the halogen atom in the above-mentioned substituent group S include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0044] In the above formula (1), Y １ and Y ２ are each independently -CR Ｙ１ = or -N=. Ｙ１ represents a hydrogen atom or a substituent. １ and Y ２ are each independently -CR Ｙ１ = is preferably represented. Examples of the substituent include the substituents exemplified for the substituent W described above, and are preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group which may have a substituent, a cyano group, or a halogen atom, and are more preferably an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. Examples of the substituent that each of the groups which may have a substituent may include the substituents exemplified for the substituent W described above, and are preferably a substituent selected from the substituent group S described above.

[0045] The definitions 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 as follows: R Ｚ１ 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:

[0046] The alkyl group of the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a t-butoxy group, and a cyclopropoxy group.

[0047] The aryl group contained in the aryloxy group may be either monocyclic or polycyclic. The number of carbon atoms in the aryloxy group is preferably 5 to 18, more preferably 6 to 10, and even more preferably 6 to 8. Examples of the aryloxy group include a phenoxy group.

[0048] The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group, and is preferably a tertiary amino group. In the secondary amino group and the tertiary amino group, the substituent on the nitrogen atom is preferably a hydrocarbon group, more preferably an alkyl group (preferably having 1 to 5 carbon atoms) or an aryl group (preferably a phenyl group).

[0049] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred.

[0050] In the above formula (1), Ar １ represents a group represented by any one of formulas (Ar-1) to (Ar-5). As described above, * in formulas (Ar-1) to (Ar-5) represents a bonding position, but the direction of the bond is not particularly limited. Of the multiple carbon atoms marked with *, either the carbon atom on the right side or the carbon atom on the left side as viewed in the paper corresponds to -C(=A ２ ) R ２In order to achieve the effects of the present invention more effectively, Ar １ is preferably a group represented by formula (Ar-1), a group represented by formula (Ar-2), or a group represented by formula (Ar-5), and more preferably a group represented by formula (Ar-1) or a group represented by formula (Ar-2).

[0051]

[0052] In formula (Ar-1), Y ３ ~Y ６ are each independently -CR Ｙ２ = or -N=, and the effect of the present invention is more excellent. ３ ~Y ６ are each independently -CR Ｙ２ It is preferred that Y represents ≡ ３ ~Y ６ When at least one of the groups represents -N=, Y ３ ~Y ６ Preferably, one or two of the groups represent -N=, and more preferably one of the groups represents -N=. ３ represents a sulfur atom, an oxygen atom, or a selenium atom, and is preferably a sulfur atom or an oxygen atom. ７ and Y ８ are each independently -CR Ｙ２ = or -N=, and the effect of the present invention is more excellent. ７ and Y ８ are each independently -CR Ｙ２ It is preferred that Y represents ≡ ７ and Y ８ When at least one of the groups represents -N=, Y ７ and Y ８ In formula (Ar-3), it is more preferable that one of Y represents -N=. ９ ~Y １４ are each independently -CR Ｙ２ = or -N=, and the effect of the present invention is more excellent. ９ ~Y １４ are each independently -CR Ｙ２ It is preferred that Y represents ≡ ９ ~Y １４When at least one of the groups represents -N=, Y ９ ~Y １４ Preferably, one or two of the groups represent -N=, and more preferably one of the groups represents -N=. ４ represents a sulfur atom, an oxygen atom, or a selenium atom, and is preferably a sulfur atom or an oxygen atom. １５ ~Y １８ are each independently -CR Ｙ２ = or -N=, and the effect of the present invention is more excellent. １５ ~Y １８ are each independently -CR Ｙ２ It is preferred that Y represents ≡ １５ ~Y １８ When at least one of the groups represents -N=, Y １５ ~Y １８ In formula (Ar-5), it is preferable that one or two of X represents -N=, and it is more preferable that one represents -N=. ５ and X ６ each independently represents a sulfur atom, an oxygen atom, or a selenium atom, and is preferably a sulfur atom or an oxygen atom. １９ and Y ２０ are each independently -CR Ｙ２ = or -N=, and the effect of the present invention is more excellent. １９ and Y ２０ are each independently -CR Ｙ２ It is preferred that Y represents ≡ １９ and Y ２０ When at least one of the groups represents -N=, Y １９ and Y ２０ Preferably, one or two of these represent -N=, and more preferably, one represents -N=.

[0053] In formulas (Ar-1) to (Ar-5), R Ｙ２represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W described above, and are preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group which may have a substituent, a cyano group, or a halogen atom, and more preferably an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. Ｙ２ The definition and preferred embodiments of each substituent represented by R Ｙ１ Examples of the substituent that may be possessed by each of the groups that may have a substituent include the substituents exemplified for the substituent W described above, and a substituent selected from the substituent group S described above is preferred.

[0054] In the above formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. In terms of the effects of the present invention being more excellent, R １ and R ２ is preferably a hydrogen atom.

[0055] In the above formula (1), A １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). １ and A ２ are each preferably independently a group represented by formula (A-1). １ and A ２ may be the same or different from each other, but are preferably the same from each other.

[0056]

[0057] In formula (A-1), * represents a bonding position.

[0058] In formula (A-1), C １ represents a ring containing two or more carbon atoms and which may have a substituent. １The two carbon atoms contained in are the two carbon atoms specified in formula (A-1). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the two carbon atoms specified in the formula. The ring may be either an aromatic ring or a non-aromatic ring. The ring may be either a monocyclic or polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms in the ring is preferably 0 to 10, and more preferably 0 to 5. １ Among the carbon atoms constituting the ring represented by the formula (A-1), the carbon atom at the bonding position marked with * and W １ Carbon atoms other than the carbon atom bonded to may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0059] Above C １ Examples of the substituent that the ring represented by the formula (I) may have include the groups exemplified for the substituent W above, and a halogen atom, an alkyl group, an aromatic ring group, a cyano group, or a silyl group is preferred, with a halogen atom or 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 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0060] 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.

[0061] In formula (A-1), W １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ２ , or =CR Ｗ３ R Ｗ４ Represents W. 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. Ｗ２ represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified above as the substituent W. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ or -CORＷ７ Represents R Ｗ５ ~R Ｗ７ 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 aliphatic hydrocarbon group is defined as above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The aromatic ring group is defined as above, and an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. The aliphatic heterocyclic group is defined as above, and the heteroatom contained in the aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. R Ｗ５ ~R Ｗ７ Examples of the substituent that each group represented by the following formula may have include the substituents exemplified for the substituent W above.

[0062] The group represented by formula (A-1) is preferably a group represented by formula (A-3) in that the effects of the present invention are more excellent.

[0063]

[0064] In formula (A-3), * represents a bonding position.

[0065] In formula (A-3), C ２ represents a ring containing at least three carbon atoms, which may have a substituent. ２The three carbon atoms contained in 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 have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5. ２ Among the carbon atoms constituting the ring represented by the formula (A-3), the carbon atom at the bonding position marked with * and Y ２ or Y ３ A carbon atom other than the carbon atom bonded to the ring C may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S). １ The substituents are the same as those that may be possessed by the group.

[0066] In formula (A-3), W ２ and W ３ each independently represents an oxygen atom or a sulfur atom, and an oxygen atom is preferred in that the effects of the present invention are more excellent.

[0067] It is more preferable that the groups represented by formula (A-1) are each independently a group represented by formula (C-1) or formula (C-2).

[0068]

[0069] In formula (C-1), X ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ or =CR Ｗ３ R Ｗ４Represents R Ｗ２ ~R Ｗ４ The definition and preferred embodiments of X are as described above for formula (A-1). ｃ１ and X ｃ２ is preferably an oxygen atom, and X ｃ１ and X ｃ２ is more preferably an oxygen atom.

[0070] 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. The number of ring atoms 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 atoms 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, and an aromatic hydrocarbon ring is preferred. The above C ３ The aromatic ring represented by the formula (I) is as described above, and is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyridine ring, a thienothiophene ring, a benzothiophene ring, a benzofuran ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring, more preferably a benzene ring, a naphthalene ring, or a thiophene ring, and 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.

[0071] In formula (C-2), X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ or =CR Ｗ３ R Ｗ４ Represents R Ｗ２ ~R Ｗ４ The definition and preferred embodiments of X are as described above for formula (A-1). ｃ３ and X ｃ４ is preferably an oxygen atom, and X ｃ３ ~Xｃ５ is more preferably an oxygen atom.

[0072] In formula (C-2), R ｃ１ and R ｃ２ 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.

[0073] In formula (A-2), R ａ１ and R ａ２ each independently represents a cyano group, —COOR ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents R ｂ１ ~R ｂ４ 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 Preferably, either one of R is a cyano group. ｂ１ ~R ｂ４ The definitions and preferred embodiments of each group represented by R Ｗ５ ~R Ｗ７ The aliphatic hydrocarbon group in the aliphatic hydrocarbon group which may have a substituent is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms. The aromatic ring group in the aromatic ring group which may have a substituent is preferably an aromatic hydrocarbon group, more preferably a phenyl group. The aliphatic heterocyclic group in the aliphatic heterocyclic group which may have a substituent is preferably an aliphatic heterocyclic group having 1 to 5 carbon atoms. Rｂ１ ~R ｂ４ Examples of the substituent that each group represented by the following formula may have include the substituents exemplified for the substituent W above.

[0074] Specific examples of the specific compounds are shown below, but the present invention is not limited to these.

[0075]

[0076]

[0077] In the specific compounds exemplified above, R, X, Y, Z, W, and V are defined as follows. X represents a sulfur atom, an oxygen atom, or a selenium atom. When multiple Xs are present in one structure, the multiple Xs may be the same or different. Y, Z, W, and V each independently represent a hydrogen atom or a group selected from the following substituent group G. Of Y, Z, W, and V, preferably two or more are hydrogen atoms, and preferably three or more are hydrogen atoms. Alternatively, Y, Z, W, and V may all be hydrogen atoms. Substituent group G: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, fluorine atom, chlorine atom, trifluoromethyl group, and m-xylyl group. R represents a group selected from the above substituent group G, or any of the following groups.

[0078]

[0079] In the specific compounds exemplified above, A represents any of the following groups: Two A's may be the same or different.

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] The molecular weight of the specific compound is preferably 400 to 1200, more preferably 400 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.

[0086] The specific compound preferably has an ionization potential of −5.0 to −6.0 eV in a single film from the viewpoints of stability when used as a p-type organic semiconductor and matching of the energy level with an n-type organic semiconductor.

[0087] The maximum absorption wavelength of the specific compound is preferably in the wavelength range of 450 to 750 nm, more preferably in the range of 500 to 700 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.

[0088] 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.

[0089] The specific compound may be purified as necessary. Examples of methods for purifying the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.

[0090] The content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound in terms of a single layer / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75% by volume, more preferably 10 to 50% by volume, and even more preferably 15 to 40% by volume. Only one type of specific compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.

[0091] <n-Type Organic Semiconductor> The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the specific compound. The n-type organic semiconductor is a compound different from the specific compound. The n-type organic semiconductor is an acceptor organic semiconductor material (compound) and refers to an organic compound that has the property of easily accepting electrons. In other words, the n-type organic semiconductor refers to the organic compound that has a larger electron affinity when two organic compounds are used in contact with each other. In other words, any organic compound can be used as the acceptor organic semiconductor as long as it is an organic compound with electron-accepting properties. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; fused aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole). ), polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic 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 dianhydride; 3,4,9,10-perylenetetracarboxylic diimide derivatives; and the compounds described in paragraphs

[0056] to

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

[0092] 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.

[0093] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0094] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less or in the range of 500 to 600 nm.

[0095] The photoelectric conversion film preferably has a bulk heterostructure formed in a state in which a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in the photoelectric conversion film in which a specific compound and an n-type organic semiconductor are mixed and dispersed. The photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs

[0013] to

[0014] of JP 2005-303266 A.

[0096] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0097] 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%.

[0098] 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.

[0099] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor) x 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume. When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the p-type organic semiconductor) x 100) is preferably 10 to 75% by volume, more preferably 15 to 50% by volume. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and a p-type organic semiconductor that is included as desired. "Substantially" means that the total content of the specific compound, n-type organic semiconductor, and p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume.

[0100] <p-Type Organic Semiconductor> The photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the specific compound. The p-type organic semiconductor is a compound different from the specific compound. The p-type organic semiconductor is a donor organic semiconductor material (compound) and refers to an organic compound that has the property of easily donating electrons. In other words, the p-type organic semiconductor refers to the organic compound that has a smaller ionization potential when two organic compounds are used in contact with each other. The p-type organic semiconductor may be used alone or in combination of two or more types.

[0101] 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] Benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of JP2018-014474A, compounds described in paragraphs

[0043] to

[0045] of WO2016 / 194630A, compounds described in paragraphs

[0025] to

[0037] and

[0099] to

[0109] of WO2017 / 159684A, compounds described in paragraphs

[0029] to

[0034] of JP2017-076766A, compounds described in paragraphs

[0015] to

[0025] of WO2018 / 207722A, and compounds described in paragraph [00 45] to

[0053] , compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

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

[0044] to

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

[0041] to

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

[0034] to

[0037] of JP2019-050398A,Compounds described in paragraphs

[0033] to

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

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

[0019] to

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

[0031] to

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

[0036] to

[0041] of JP-A No. 2018-166200 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, and paragraphs of JP-A No. 2018-014474

[0031] to

[0036] compounds described in paragraphs

[0036] to

[0046] of WO2018 / 016465, and compounds described in paragraphs

[0045] to

[0048] of JP-A-2020-010024, 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-2022-123944), dicarbazole compounds (for example, compounds described in Figures 2 to 5 of JP-A-2022-122839), benzoquinazoline compounds (for example, compounds described in paragraphs

[0053] to

[0056] of JP-A-2022-120323),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 [00 73] and the compounds described in paragraph

[0028] of JP-A No. 2022-100258), triscarbazolylphenyl compounds (for example, the compounds described in paragraphs

[0038] to

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

[0070] to

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

[0051] to

[0064] of JP-A No. 2021-163968. Examples of p-type organic semiconductors include compounds having a smaller ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are listed below.

[0102]

[0103]

[0104]

[0105]

[0106] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0107] 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%.

[0108] 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.

[0109] <Dye> The photoelectric conversion film preferably contains a dye in addition to the specific compound. The dye is a compound different from the specific compound. The dye is preferably an organic dye. Examples of the organic dye include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, and benzophenone dyes. Examples of the organic dye include clidinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, imidazoquinoxaline dyes described in WO 2020 / 013246, WO 2022 / 168856, JP 2023-10305 A, and JP 2023-10299 A, as well as 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, and acceptor-donor-acceptor type dyes are preferred as organic dyes.

[0110] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and even more preferably in the wavelength range of 450 to 650 nm.

[0111] The content of the dye relative to the total content of the specific compound and the dye in the photoelectric conversion film (= (film thickness of the dye in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the dye in terms of a single layer)×100)) is preferably 5 to 75 vol%, more preferably 5 to 60 vol%, and still more preferably 5 to 50 vol%.

[0112] <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.

[0113] 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.

[0114] [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); metal thin films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and nanocarbon materials such as carbon nanotubes and graphene. Of these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0115] 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 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.

[0116] Depending on the application, the lower electrode 11 may be made transparent or may be made non-transparent and reflect light. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.

[0117] 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.

[0118] [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.

[0119] <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, and diacetylene, as well as derivatives thereof.

[0120] 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.

[0121] <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.

[0122] Examples of methods for producing a charge blocking film include dry film formation and wet film formation. Examples of dry film formation methods 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 methods 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.

[0123] 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.

[0124] [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.

[0125] [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.

[0126] [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.

[0127] [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. A manufacturing method for an imaging element is not particularly limited, but examples include a method including the step of manufacturing the photoelectric conversion element described above.

[0128] [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.

[0129] [Compound] The present invention also includes inventions of specific compounds.

[0130] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0131] [Compounds used in photoelectric conversion film] The materials used in the photoelectric conversion film are listed below.

[0132] [Synthesis of Compound (1-1)] Compound (1-1) was synthesized according to the following scheme.

[0133]

[0134] Compound (1-1-1) (2.0 mmol), compound (1-1-2) (5.0 mmol), toluene (60 mL), and piperidine (0.02 mmol) were placed in a glass reaction vessel and reacted at 100°C for 2 hours under a nitrogen atmosphere. The precipitated solid was filtered, and the resulting solid was washed successively with tetrahydrofuran (THF), N,N-dimethylacetamide (DMAc), and THF, followed by purification by sublimation to obtain 1.0 mmol of compound (1-1) (yield: 50%). The structure of compound (1-1) was confirmed by LDI-MS (laser desorption ionization mass spectrometry). LDI-MS (compound (1-1)): 545 (M ＋ )

[0135] The compounds used in the photoelectric conversion film of each of the Examples and Comparative Examples other than the compound (1-1) were synthesized according to the synthesis method of the compound (1-1).

[0136] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for comparison are listed below. Compounds (1-1) to (1-29) are specific compounds, and compounds (C-1) to (C-4) are comparative compounds.

[0137]

[0138]

[0139]

[0140] [n-type organic semiconductor] Fullerene (C ６０ )

[0141] [p-type organic semiconductor]

[0142]

[0143] [Evaluation] The photoelectric conversion element was evaluated for quantum efficiency, electric field strength dependency of quantum efficiency, response speed, and electric field strength dependency of response speed when receiving red and green light by the following methods.

[0144] [Fabrication of Photoelectric Conversion Element] A photoelectric conversion element having the configuration shown in FIG. 2 was fabricated 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 temperature of the glass substrate controlled at 25° C., 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 (D-1) were co-deposited by vacuum deposition in a ratio of 1:1:1 in terms of a single layer, respectively, to form a film. This resulted in a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. Furthermore, 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.

[0145]

[0146] [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.

[0147] [Quantum Efficiency] The quantum efficiency of each photoelectric conversion element was measured when red and green light was received 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 1-12)

[0148] A: Quantum efficiency (relative ratio) is 1.5 or more. B: Quantum efficiency (relative ratio) is 1.2 or more and less than 1.5. C: Quantum efficiency (relative ratio) is 1.0 or more and less than 1.2. D: Quantum efficiency (relative ratio) is less than 1.0.

[0149] [Dependence of Quantum Efficiency on Electric Field Strength] For each photoelectric conversion element, the dependence of quantum efficiency on electric field strength when red and green light was received was evaluated by the following method. ４ The quantum efficiency (photoelectric conversion efficiency) at 7.5 V / cm 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. The electric field strength dependency of the quantum efficiency is preferably rated C or higher. Formula (S2): Electric field strength dependency of quantum efficiency = (electric field strength of each photoelectric conversion element 7.5 × 10 ４ V / cm) / (electric field strength of each photoelectric conversion element 2.0×10 ５ Quantum efficiency in V / cm

[0150] 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 0.6 or more and less than 0.7.

[0151] [Response Speed] The response speed of each photoelectric conversion element when receiving red and green light 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. The response speed is preferably evaluated as C or higher. Formula (S3): Relative response speed = (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element of Examples 1-12)

[0152] A: Relative response speed is less than 0.6 B: Relative response speed is 0.6 or more and less than 0.8 C: Relative response speed is 0.8 or more and less than 1.2 D: Relative response speed is 1.2 or more

[0153] [Dependence of response speed on electric field strength] For each photoelectric conversion element, the dependence of the response speed on electric field strength when red and green light was received was evaluated by the following method. 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. In formula (S4), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. The electric field strength dependency of the response speed is preferably rated B or higher. Formula (S4): Electric field strength dependency of response speed = (electric field strength of each photoelectric conversion element 7.5 × 10 ４ V / cm) / (electric field strength of each photoelectric conversion element 2.0×10 ５ rise time in V / cm)

[0154] A: The electric field strength dependency of the response speed is less than 3.0. B: The electric field strength dependency of the response speed is 3.0 or more and less than 5.0. C: The electric field strength dependency of the response speed is 5.0 or more.

[0155] [Results] The evaluation results of Test X are shown in Table 1 below. １ ~Y ２０ " column indicates the specific compound (compound represented by formula (1)) in which Y １ and Y ２ are each independently -CR Ｙ１ =, and Y ３ ~Y ２０ are each independently -CR Ｙ２ In the table, "X" is used to indicate the difference between the two values. １ and X ２ " column indicates the X １ and X ２ One of them is -NR Ｚ１ - and the other represents a sulfur atom or an oxygen atom, it is represented as "A", and in other cases it is represented as "B". １ " column indicates the presence of Ar in a specific compound. １ is a group represented by formula (Ar-1) or a group represented by formula (Ar-2), it is represented as "A", and in other cases it is represented as "B". Ｚ１ (1)" column indicates the specific compound in which R Ｚ１ is a group selected from the group consisting of linear aliphatic hydrocarbon groups having 1 to 2 carbon atoms which may have a halogen atom, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms which may have a halogen atom, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms which may have a halogen atom, and aromatic ring groups having 4 to 10 carbon atoms which may have a substituent, and is represented by "A", and in other cases it is represented by "B". Ｚ１ (2)" column indicates the specific compound in which R Ｚ１ is a group selected from the group consisting of a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent, it is designated as "A", and in other cases it is designated as "B". １ and A ２are each independently a group represented by formula (A-1), it is represented as "A", and in other cases it is represented as "B". In the table, the column "Formula (C-1) or Formula (C-2)" indicates that in a specific compound, A １ and A ２ are each independently a group represented by formula (C-1) or formula (C-2), the result is "A", and in other cases the result is "B". In the table, "-" indicates that no evaluation was performed.

[0156]

[0157] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention has a small electric field strength dependency of the quantum efficiency for red and green light. It was also confirmed that the photoelectric conversion element of the present invention is excellent in the quantum efficiency for red and green light, the response speed, and the electric field strength dependency of the response speed.

[0158] From the comparison of Examples 1-13 to 1-24, it was found that in the specific compound (compound represented by formula (1)), Y １ and Y ２ are each independently -CR Ｙ１ =, and Y ３ ~Y ２０ are each independently -CR Ｙ２ It was confirmed that when X = 1, the quantum efficiency, the electric field strength dependency of the quantum efficiency, the response speed, and the electric field strength dependency of the response speed for red and green light were superior. １ and X ２ One of them is -NR Ｚ１ It was confirmed that when one atom represents a sulfur atom or an oxygen atom, the quantum efficiency, the electric field strength dependence of the quantum efficiency, the response speed, and the electric field strength dependence of the response speed for red-green light were superior. １ is a group represented by formula (Ar-1) or a group represented by formula (Ar-2), it was confirmed that the quantum efficiency, the electric field strength dependence of the quantum efficiency, the response speed, and the electric field strength dependence of the response speed for red-green light were more excellent. Ｚ１is a group selected from the group consisting of linear aliphatic hydrocarbon groups having 1 to 2 carbon atoms which may have a halogen atom, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms which may have a halogen atom, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms which may have a halogen atom, and aromatic ring groups having 4 to 10 carbon atoms which may have a substituent, the quantum efficiency, the electric field strength dependency of the quantum efficiency, and the response speed for red and green light are more excellent, and R Ｚ１ is a group selected from the group consisting of a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, and an aromatic ring group having 4 to 10 carbon atoms which may have a substituent, it was confirmed that the quantum efficiency, the electric field strength dependence of the quantum efficiency, the response speed, and the electric field strength dependence of the response speed for red-green light are more excellent. １ and A ２ are each independently a group represented by formula (C-1) or formula (C-2), it has been confirmed that the quantum efficiency, the electric field strength dependence of the quantum efficiency, the response speed, and the electric field strength dependence of the response speed for red-green light are more excellent.

[0159] [Evaluation: Test Y] Subsequently, in addition to the specific compound, a photoelectric conversion element was prepared using the following dyes (B-1) to (B-9) other than the specific compound. Specifically, a photoelectric conversion element was prepared by combining any one of the compounds (1-1), (1-2), (1-8), (1-10), (1-13), (1-18), (1-22), and (1-29), any one of the dyes (B-1) to (B-9), and an n-type organic semiconductor (fullerene (C ６０)) and a p-type organic semiconductor (D-1) were co-deposited by vacuum deposition to form a film in a ratio of compound (specific compound or comparative compound):dye:p-type organic semiconductor:n-type organic semiconductor = 1:1:2:2 in terms of a single film, thereby forming a photoelectric conversion film 12 with a thickness of 240 nm. The remaining procedures were the same as in Test X above, and photoelectric conversion elements of each example were produced. Subsequently, the various evaluations described above were carried out using each of the obtained photoelectric conversion elements. As a result, it was confirmed that even when photoelectric conversion elements were produced using the dyes (B-1) to (B-9) shown below in addition to the specific compound, the results were equivalent to those of the examples shown in Table 1.

[0160] [Pigment]

[0161]

[0162] 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). In formula (1), Y １ and Y ２ Each independently represents -CR Ｙ１ = or -N=. Ｙ１ represents a hydrogen atom or a substituent. １ and X ２ One of them is -NR Ｚ１ -, and the other represents a sulfur atom, an oxygen atom, or a selenium atom. Ｚ１ 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. １ represents a group represented by any one of formulas (Ar-1) to (Ar-5). n represents 0 or 1. １ and R ２ Each of A and B independently represents a hydrogen atom or a substituent. １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). ３ ~Y ６ Each independently represents -CR Ｙ２ In formula (Ar-2), X represents -N= or -N=. ３ represents a sulfur atom, an oxygen atom, or a selenium atom. ７ and Y ８ Each independently represents -CR Ｙ２ In formula (Ar-3), Y represents -N= or -N=. ９ ~Y １４ Each independently represents -CR Ｙ２ In formula (Ar-4), X represents -N= or -N=. ４ represents a sulfur atom, an oxygen atom, or a selenium atom. １５ ~Y １８ Each independently represents -CR Ｙ２ In formula (Ar-5), X represents -N= or -N=. ５ and X ６ each independently represents a sulfur atom, an oxygen atom, or a selenium atom. １９ and Y ２０ Each independently represents -CR Ｙ２ In formulae (Ar-1) to (Ar-5), R Ｙ２ represents a hydrogen atom or a substituent. １ represents a ring containing two or more carbon atoms and which may have a substituent. １ is a sulfur atom, an oxygen atom, ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents R Ｗ５ ~R Ｗ７ 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 each independently represents a cyano group, -COOR ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents R ｂ１ ~R ｂ４ 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. * represents a bonding position.

2. Y １ and Y ２ Each independently represents -CR Ｙ１ =, and Y ３ ~Y ２０ Each independently represents -CR Ｙ２ The photoelectric conversion element according to claim 1 , wherein:

3. X １ and X ２ One of them is -NR Ｚ１ 2. The photoelectric conversion element according to claim 1, wherein one of the groups represents -, and the other represents a sulfur atom or an oxygen atom.

4. Ar １ is a group represented by formula (Ar-1) or a group represented by formula (Ar-2).

5. R Ｚ１ is a group selected from the group consisting of linear aliphatic hydrocarbon groups having 1 to 2 carbon atoms which may have a halogen atom, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms which may have a halogen atom, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms which may have a halogen atom, and aromatic ring groups having 4 to 10 carbon atoms which may have a substituent.

6. R Ｚ１ is a group selected from the group consisting of branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms which may have a halogen atom, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms which may have a halogen atom, and aromatic ring groups having 4 to 10 carbon atoms which may have a substituent.

7. A １ and A ２ are each independently a group represented by formula (A-1).

8. The photoelectric conversion element according to claim 7, wherein the groups represented by formula (A-1) are each independently 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, or ═NR Ｗ２ Or = CR Ｗ３ R Ｗ４ Represents ３ In formula (C-2), X represents an aromatic ring which may have a substituent. ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ Or = CR Ｗ３ R Ｗ４ Represents Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ 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. ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent. * represents a bonding position.

9. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed in a state in which the compound represented by formula (1) and the n-type organic semiconductor are mixed.

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

11. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion film further contains a p-type organic semiconductor.

12. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion film further contains a dye.

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

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

15. An optical sensor comprising the photoelectric conversion element according to any one of claims 1 to 13.

16. A method for manufacturing an imaging element, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 13.

17. A compound represented by formula (1). In formula (1), Y １ and Y ２ Each independently represents -CR Ｙ１ = or -N=. Ｙ１ represents a hydrogen atom or a substituent. １ and X ２ One of them is -NR Ｚ１ -, and the other represents a sulfur atom, an oxygen atom, or a selenium atom. Ｚ１ 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. １ represents a group represented by any one of formulas (Ar-1) to (Ar-5). n represents 0 or 1. １ and R ２ Each of A and B independently represents a hydrogen atom or a substituent. １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). ３ ~Y ６ Each independently represents -CR Ｙ２ In formula (Ar-2), X represents -N= or -N=. ３ represents a sulfur atom, an oxygen atom, or a selenium atom. ７ and Y ８ Each independently represents -CR Ｙ２ In formula (Ar-3), Y represents -N= or -N=. ９ ~Y １４ Each independently represents -CR Ｙ２ In formula (Ar-4), X represents -N= or -N=. ４ represents a sulfur atom, an oxygen atom, or a selenium atom. １５ ~Y １８ Each independently represents -CR Ｙ２ In formula (Ar-5), X represents -N= or -N=. ５ and X ６ each independently represents a sulfur atom, an oxygen atom, or a selenium atom. １９ and Y ２０ Each independently represents -CR Ｙ２ In formulae (Ar-1) to (Ar-5), R Ｙ２ represents a hydrogen atom or a substituent. １ represents a ring containing two or more carbon atoms and which may have a substituent. １ is a sulfur atom, an oxygen atom, ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ 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 each independently represents a cyano group, -COOR ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents ｂ１ ~R ｂ４ 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. * represents a bonding position.

18. Y １ and Y ２ Each independently represents -CR Ｙ１ =, and Y ３ ~Y ２０ Each independently represents -CR Ｙ２ 18. The compound according to claim 17, wherein:

19. X １ and X ２ One of them is -NR Ｚ１ The compound according to claim 17, wherein each of the groups represents -, and the other represents a sulfur atom or an oxygen atom.

20. Ar １ is a group represented by formula (Ar-1) or a group represented by formula (Ar-2).

21. R Ｚ１ is a group selected from the group consisting of linear aliphatic hydrocarbon groups having 1 to 2 carbon atoms which may have a halogen atom, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms which may have a halogen atom, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms which may have a halogen atom, and aromatic ring groups having 4 to 10 carbon atoms which may have a substituent.

22. R Ｚ１ is a group selected from the group consisting of branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms which may have a halogen atom, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms which may have a halogen atom, and aromatic ring groups having 4 to 10 carbon atoms which may have a substituent.

23. A １ and A ２ are each independently a group represented by formula (A-1).

24. The compound according to claim 23, wherein the groups represented by formula (A-1) are each independently 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, or ═NR Ｗ２ Or = CR Ｗ３ R Ｗ４ Represents ３ In formula (C-2), X represents an aromatic ring which may have a substituent. ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ Or = CR Ｗ３ R Ｗ４ Represents Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ or -COR Ｗ７ Represents R Ｗ５ ~R Ｗ７ 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. ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent. * represents a bonding position.

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