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

Abstract

Provided are: a photoelectric conversion element in which the dependency of quantum efficiency on electric field intensity with respect to blue-green light is low; and an imaging element, an optical sensor, a method for manufacturing the imaging element, and a compound which are related to the photoelectric conversion element. The photoelectric conversion element according to the present invention comprises an electroconductive film, a photoelectric conversion film, and a transparent electroconductive film, in this order. The photoelectric conversion film contains a compound expressed by any one of the formulae (1-1) to (1-3). CA represents a ring represented by one of the formulae (2-1)-(2-3).　CC represents a ring represented by formula (5).　A represents a group represented by formula (A-1).

Description

Photoelectric conversion element, image sensor, light sensor, method for manufacturing an image sensor, compound

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

[0002] In recent years, the development of devices having photoelectric conversion films (for example, image sensors) has progressed. For example, Patent Document 1 discloses a photoelectric conversion device that exhibits excellent high photoelectric conversion efficiency and low dark current even when subjected to heat treatment, comprising, in this order, a conductive film, a photoelectric conversion film containing a photoelectric conversion material, and a transparent conductive film, wherein the photoelectric conversion material contains a compound (A) represented by formula (1).

[0003] Japanese Patent Publication No. 2014-080417

[0004] With the increasing demand for improved performance in image sensors and optical sensors, there is a need for photoelectric conversion elements that exhibit superior characteristics. One characteristic required of a photoelectric conversion element is that its sensitivity does not change significantly when the electric field strength is changed; in other words, its quantum efficiency has low dependence on electric field strength. Under these requirements, 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 blue-green light had high dependence on electric field strength, indicating room for improvement. In this specification, blue-green light refers to light with a wavelength of 400 to 530 nm.

[0005] Therefore, the present invention aims to provide a photoelectric conversion element in which the dependence of quantum efficiency on electric field strength for blue-green light is small. Furthermore, the present invention also aims to provide an image sensor, a light sensor, a method for manufacturing an image sensor, and a compound related to the above-mentioned photoelectric conversion element.

[0006] As a result of diligent research to solve the above problems, the 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 that order, wherein the photoelectric conversion film contains a compound represented by any of the formulas (1-1) to (1-3) described later. [2] The photoelectric conversion element according to [1], wherein A in formula (5) described later is a group represented by formula (C-1) described later, or a group represented by formula (C-2) described later. [3] The photoelectric conversion element according to [1] or [2], wherein the compound represented by formula (1-1) satisfies at least one of the requirements A and D described later, the compound represented by formula (1-2) satisfies at least one of the requirements A, B and D described later, and the compound represented by formula (1-3) satisfies at least one of the requirements A to D described later. [4] The photoelectric conversion element according to any one of [1] to [3], wherein the photoelectric conversion film contains a compound represented by formula (1-1). [5] In the above formulas (1-1) to (1-3), C ＡThe photoelectric element according to any one of [1] to [4], wherein the photoelectric film is a ring represented by formula (2-1) above. [6] The photoelectric element according to any one of [1] to [5], wherein the photoelectric film further comprises an n-type organic semiconductor, and the photoelectric film has a bulk heterostructure formed when a compound represented by any one of formulas (1-1) to (1-3) above and the n-type organic semiconductor are mixed. [7] The photoelectric element according to [6], wherein the n-type organic semiconductor comprises fullerenes selected from the group consisting of fullerenes and their derivatives. [8] The photoelectric element according to any one of [1] to [7], wherein the photoelectric film further comprises a p-type organic semiconductor. [9] The photoelectric element according to any one of [1] to [8], wherein the photoelectric film further comprises a dye.

[10] A photoelectric conversion element according to any one of [1] to [9], wherein A has one or more intermediate layers between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film.

[11] An image sensor having the photoelectric conversion element according to any one of [1] to

[10] .

[12] A light sensor having the photoelectric conversion element according to any one of [1] to

[10] .

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

[10] .

[14] A compound represented by any of the formulas (1-1) to (1-3) described later.

[15] The compound according to

[14] , wherein A in formula (5) described later is a group represented by formula (C-1) described later, or a group represented by formula (C-2) described later.

[16] The compound according to

[14] or

[15] , wherein the compound represented by formula (1-1) satisfies at least one of the requirements A and D described later, the compound represented by formula (1-2) satisfies at least one of the requirements A, B and D described later, and the compound represented by formula (1-3) satisfies at least one of the requirements A to D described later.

[17] The compound according to any one of

[14] to

[16] , represented by formula (1-1).

[18] In formulas (1-1) to (1-3), C Ａ However, the compound is one of the compounds listed in any one of

[14] to

[17] , which is a ring represented by the above formula (2-1).

[0008] According to the present invention, a photoelectric conversion element can be provided in which the dependence of the quantum efficiency on the electric field strength for blue-green light is small. Furthermore, according to the present invention, an image sensor, a light sensor, a method for manufacturing the image sensor, and a compound related to the above-mentioned photoelectric conversion element can also be provided.

[0009] This is a schematic cross-sectional diagram showing one example of the configuration of a photoelectric conversion element.

[0010] The present invention will be described in detail below. The following descriptions of constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0012] In this specification, a hydrogen atom may be either a light hydrogen atom (a normal hydrogen atom) or a deuterium atom (for example, a double hydrogen atom). In this specification, when there are multiple substituents and linking groups, etc. (hereinafter also referred to as "substituents, etc.") indicated by a specific symbol, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. may be identical or different from the others. The same applies to the specification of the number of substituents, etc.

[0013] In this specification, unless otherwise specified, "substituent" refers to the group exemplified by the substituent W below.

[0014] (Substituent W) The substituent W in this specification is described below. Substituents W include, for example, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), alkyl groups (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (heteroaryl groups and aliphatic heterocyclic groups), cyano groups, nitro groups, alkoxy groups, aryloxy groups, silyl groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, alkoxycarbonyloxy groups, and aryl groups. Examples include hydroxycarbonyloxy groups, primary, secondary, or tertiary amino groups (including anilino groups), alkylthio groups, arylthio groups, heterocyclic thio groups, alkyl or arylsulfinyl groups, alkyl or arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, phosphoric acid groups, hydroxyl groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, and others. Each of the above groups may, if possible, have further substituents (for example, one or more of the above groups). For example, an alkyl group which may have substituents is also included as one form of substituent W. If substituent W has carbon atoms, the number of carbon atoms in substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms in substituent W is, for example, 1 to 30. The specific compounds described later may have the following substituents: hydroxyl group, thiol group, acylamino group, carbamoyl group, ureido group, boronic acid group (-B(OH) ２ ) and / or the absence of a primary amino group is also preferable.

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

[0017] In this specification, unless otherwise specified, the alkyl portion of the alkoxy group and alkylthio group is preferably the alkyl group described above. In an alkoxy group which may have substituents, examples of substituents that the alkoxy group may have are the same as examples of substituents in an alkyl group which may have substituents. In an alkylthio group which may have substituents, examples of substituents that the alkylthio group may have are the same as examples of substituents in an alkyl group which may have substituents.

[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 an alkenyl group which may have substituents, examples of substituents that the alkenyl group may have are the same as examples of substituents in an alkyl group which may have substituents. 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 an alkynyl group which may have substituents, examples of substituents that the alkynyl group may have are the same as examples of substituents in an alkyl group which may have substituents.

[0019] In this specification, unless otherwise specified, the aromatic ring or aromatic ring group may be monocyclic or polycyclic (e.g., 2 to 6 rings). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as its ring structure. A polycyclic (e.g., 2 to 6 rings) aromatic ring has a fused ring structure containing multiple monocyclic aromatic rings (e.g., 2 to 6). The monocyclic aromatic ring is preferably a 5-membered or 6-membered ring. Furthermore, the polycyclic aromatic ring is preferably a fused ring structure containing multiple monocyclic aromatic rings selected from 5-membered and 6-membered rings (e.g., 2 to 6). It is also preferable that the polycyclic aromatic ring consists of a fused ring of monocyclic aromatic rings. Unless otherwise specified, the number of ring member atoms in the above aromatic ring is preferably 5 to 20. In this specification, the "number of ring member atoms" in a ring (aromatic rings, alicyclic rings, etc.) refers to the number of atoms constituting the ring structure, and in the case of polycyclic rings, it refers to the number of atoms constituting the polycyclic ring. 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 it has as ring member atoms is, for example, 1 to 10. Examples of the heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron. Examples of the aromatic hydrocarbon rings include benzene, naphthalene, anthracene, pyrene, phenanthrene, and fluorene rings.Examples of the above aromatic heterocycles include pyridine rings, pyrimidine rings, pyridazine rings, pyrazine rings, triazine rings (e.g., 1,2,3-triazine rings, 1,2,4-triazine rings and 1,3,5-triazine rings, etc.), tetrazine rings (e.g., 1,2,4,5-tetrazine rings, etc.), quinoxaline rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, benzopyrrole rings, benzofuran rings, benzothiophene rings, benzimidazole rings, benzoxazole rings, benzothiazole rings, naphthopyrrole rings, naphthofuran rings, naphthothiophene rings, naphtoimidazole rings, naphthoxazole rings, pyrroloimidazole rings (e.g., 5H-pyrrolo[1,2-a]imidazole rings, etc.), imidazoxazole rings (e.g., imidazo[2,1-b]oxazole rings, etc.), Thienothiazole rings (e.g., thieno[2,3-d]thiazole rings, etc.), benzothiadiazole rings, benzodithiophene rings (e.g., benzo[1,2-b:4,5-b']dithiophene rings, etc.), thienothiophene rings (e.g., thieno[3,2-b]thiophene rings, etc.), thiazolothiazole rings (e.g., thiazolo[5,4-d]thiazole rings, etc.), naphthodithiophene rings (e.g., naphtho[2,3- Examples include the [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, when referring to an aromatic ring group, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic ring is included. In this specification, when referring to an aromatic hydrocarbon group, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic hydrocarbon ring is included, and when referring to an aromatic heterocyclic group, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic heterocyclic ring is included. In this specification, when referring to an aryl group, for example, a group obtained by removing one hydrogen atom from the ring corresponding to the aromatic hydrocarbon ring among the above-mentioned aromatic ring is included. In this specification, when referring to a heteroaryl group, for example, a group obtained by removing one hydrogen atom from the ring corresponding to the aromatic heterocyclic ring among the above-mentioned aromatic ring is included. In this specification, when referring to an arylene group, for example, a group obtained by removing two hydrogen atoms from the ring corresponding to the aromatic hydrocarbon ring among the above-mentioned aromatic ring is included. In this specification, when referring to a heteroarylene group, for example, it refers to a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the aromatic rings mentioned above. In an optionally substituted aromatic ring group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted arylene group, and an optionally substituted heteroarylene group, the types of substituents that these groups may have include, for example, the group exemplified by substituent W. When these groups have substituents, the number of substituents may be one or more (for example, 1 to 4, etc.).

[0021] In this specification, a non-aromatic ring refers to a ring structure that does not fall under the category of aromatic, and examples include aliphatic hydrocarbon rings and aliphatic heterocycles. Examples of aliphatic hydrocarbon rings include cycloalkanes, cycloalkenes, and cycloalkynes. Examples of aliphatic heterocycles include pyrrolidine rings, oxolane rings, thiolane rings, piperidine rings, tetrahydropyran rings, thiane rings, piperazine rings, morpholine rings, quinuclidine rings, azetidine rings, oxetane rings, aziridine rings, dioxane rings, and γ-butyrolactone rings. In this specification, when referring to an aliphatic hydrocarbon ring group, examples include a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from a ring corresponding to an aliphatic hydrocarbon ring. In this specification, when referring to an aliphatic heterocycle group, examples include a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from a ring corresponding to an aliphatic heterocycle.

[0022] In this specification, if a single formula representing a chemical structure contains multiple identical symbols indicating the type or number of groups, unless otherwise specified, the meanings of these multiple identical symbols are independent of each other, and the meanings of these identical symbols may be the same or different. In this specification, if a single formula representing a chemical structure contains multiple groups of the same kind (e.g., alkyl groups), unless otherwise specified, the specific meanings of these multiple groups of the same kind are independent of each other, and the specific meanings of these groups of the same kind may be the same or different.

[0023] In this specification, the bonding direction of the divalent group (e.g., -CO-O-) is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -CO-O-, 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, for convenience, be described in only one form, either the cis or trans isomer. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans isomer, and the compound may be in either the cis or trans form. Furthermore, in this specification, with respect to compounds having a chiral atom, the general formula or structural formula representing the compound may, for convenience, be described without distinguishing between stereoisomers. Even in such cases, unless otherwise specified, the form of the compound is not limited to either form, and may be either one form or a mixture thereof. For example, a compound having a chiral carbon atom may, unless otherwise specified, be either the S or R isomer, or a mixture thereof.

[0025] In this specification, unless otherwise specified, if there are two or more bond positions represented by * in a formula, the direction of the bond is not particularly limited. For example, in a compound represented by the formula "X-Y-Z", if Y is a group represented by *-A-B-*, the compound may be either "X-A-B-Z" or "X-B-A-Z". Also, for example, a structure in which a ring represented by formula (X1) and a ring represented by formula (X2) are fused at a bond position represented by * may be either the structure represented by formula (X3) or the structure represented by formula (X4).

[0026]

[0027] [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 that order, wherein the photoelectric conversion film contains a compound represented by any of the formulas (1-1) to (1-3) described later (hereinafter also referred to as the "specific compound").

[0028] The reason why a photoelectric conversion element having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is included within the scope of the present invention. One method for improving the electric field strength dependence of quantum efficiency in a photoelectric conversion element is to reduce the domain of the dye in the photoelectric conversion element, that is, to suppress aggregation of dyes and disperse the dye in the photoelectric conversion film, thereby shortening the exciton diffusion length of the dye. Here, the compound represented by any of formulas (1-1) to (1-3) in the present invention (specific compound) mainly functions as a dye in the photoelectric conversion film, and one of its structural features is that it has a cyclopentadiene structure adjacent to the acidic nucleus represented by A. Due to this feature, aggregation of the specific compound is suppressed by the steric hindrance group derived from the cyclopentadiene structure. Furthermore, in the specific compound, because there is only one acidic nucleus represented by A, the polar surface area of ​​the entire molecule is reduced, and the specific compound is -NR Ｎ ２ The absence of electron-donating groups represented by is also thought to contribute to suppressing aggregation of specific compounds due to dipole-dipole interactions. In summary, it is presumed that the specific compounds possessing the aforementioned structural characteristics suppress aggregation of specific compounds, thereby improving the electric field strength dependence of the quantum efficiency of the photoelectric conversion element. As a result, the photoelectric conversion element of the present invention is considered to have excellent electric field strength dependence of quantum efficiency for blue-green light. Hereinafter, a smaller electric field strength dependence of quantum efficiency for blue-green light will also be referred to as "the effect of the present invention is superior."

[0029] FIG. 1 shows a cross-sectional schematic view of an embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in FIG. 1 has a structure in which a conductive film (hereinafter also referred to as "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 "upper electrode") 15 functioning as an upper electrode are laminated in this order. FIG. 2 shows a configuration example of another photoelectric conversion element. The photoelectric conversion element 10b shown in FIG. 2 has a structure in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are laminated in this order on the lower electrode 11. Note that the lamination 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 appropriately changed according to the application and characteristics.

[0030] In the photoelectric conversion element 10a (or 10b), light is preferably 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 －５ ~1×10 ７ V / cm is preferably applied between this pair of electrodes. In terms of performance and power consumption, the applied voltage is more preferably 1×10 －４ ~1×10 ７ V / cm, and even more preferably 1×10 －３ ~5×10 ６ V / cm. Regarding the voltage application method, in FIGS. 1 and 2, it is preferable to apply the voltage so that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode. When the photoelectric conversion element 10a (or 10b) is used as an optical sensor or incorporated into an imaging element, the voltage can be applied by the same method. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably applied to imaging element applications. Hereinafter, the forms of each layer constituting the photoelectric conversion element of the present invention will be described in detail.

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

[0032] <Specific Compounds> The photoelectric conversion film contains a compound represented by any of formulas (1-1) to (1-3). The photoelectric conversion film preferably contains a compound represented by formula (1-1) or formula (1-2), and more preferably contains a compound represented by formula (1-1).

[0033]

[0034] In formula (1-1), C Ａ This represents a ring expressed by any of the equations (2-1) to (2-3). Ｃ This represents the ring shown in equation (5). Note that C Ａ A ring represented by C Ｃ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with * in formula (5). The direction of ring fusion is not particularly restricted.

[0035] In formula (1-2), C Ａ This represents a ring expressed by any of the equations (2-1) to (2-3). Ｂ１ This represents a ring expressed by any of the equations (3-1) to (3-5). Ｃ This represents the ring shown in equation (5). Note that C Ａ A ring represented by C Ｂ１ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with *1 in formulas (3-1) to (3-5). Ｂ１ A ring represented by C Ｃ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *2 in formulas (3-1) to (3-5) and the position of the carbon atom marked with * in formula (5). The direction of ring fusion is not particularly restricted.

[0036] In formula (1-3), C Ａ This represents a ring expressed by any of the equations (2-1) to (2-3). Ｂ１ This represents a ring expressed by any of the equations (3-1) to (3-5). Ｂ２ This represents a ring expressed by any of the equations (4-1) to (4-5). Ｃ This represents the ring shown in equation (5). Note that C ＡA ring represented by C Ｂ１ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with *1 in formulas (3-1) to (3-5). Ｂ１ A ring represented by C Ｂ２ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *2 in formulas (3-1) to (3-5) and the position of the carbon atom marked with *2 in formulas (4-1) to (4-5). Ｂ２ A ring represented by C Ｃ The ring represented by the formula is formed by ring fusion between the position of the carbon atom marked with *3 in formulas (4-1) to (4-5) and the position of the carbon atom marked with * in formula (5). The direction of ring fusion is not particularly restricted.

[0037] In formulas (1-1) to (1-3), C Ａ It is preferably a ring represented by formula (2-1) or formula (2-2) above, and more preferably a ring represented by formula (2-1) above. Ｂ１ It is preferably a ring represented by formula (3-1), formula (3-2), or formula (3-3) above, and more preferably a ring represented by formula (3-1) above. Ｂ２ It is preferably a ring represented by formula (4-1), formula (4-2), or formula (4-3) above, and more preferably a ring represented by formula (4-1) above.

[0038] In equations (2-1) to (2-3), (3-2), (3-3), (4-2), and (4-3), Z is independently -CR Ｚ１ = or represents a nitrogen atom. R Ｚ１ represents a hydrogen atom or a specific substituent. The specific substituent is -NR Ｎ ２ This represents a substituent that does not contain either -CH=A. Ｎ ２ "Neither -CH=A nor -CH=A is included" means that the above groups are not included as part or all of the substituents. Ｚ１ By not containing the aforementioned predetermined group, aggregation of the specific compound within the photoelectric conversion film can be suppressed, resulting in superior effects of the present invention. -NR Ｎ２ Medium, R Ｎ Each of these independently represents a hydrogen atom or a substituent. In -CH=A, A represents a group represented by formula (A-1). Formula (A-1) will be explained later.

[0039] The specific substituents are, for example, among the substituents exemplified by substituent W above, groups containing aromatic rings, halogen atoms, and -SiR groups, which exhibit superior effects of the present invention. Ｓｉ ３ Preferably, the group is an aliphatic hydrocarbon group which may have substituents, an aliphatic heterocyclic group which may have substituents, a cyano group which may have substituents, an acyl group which may have substituents, or an alkoxy group which may have substituents, as detailed later, a group represented by formula (Z), a halogen atom, -SiR Ｓｉ ３ Preferably, a substituted aliphatic hydrocarbon group, a cyano group, a substituted acyl group, or a substituted alkoxy group, a group represented by formula (Z), a halogen atom, -SiR Ｓｉ ３ More preferably, an aliphatic hydrocarbon group which may have substituents, and even more preferably, a group represented by formula (Z). The substituents which each of the above-mentioned substituents which may have substituents include, among the substituents exemplified by substituent W above, -NR Ｎ ２ Examples of substituents that do not contain either -CH=A.

[0040] Examples of groups containing an aromatic ring include an aromatic ring group obtained by removing one hydrogen atom from an aromatic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, and may be monocyclic or polycyclic. The aromatic ring may have substituents. If the aromatic ring has substituents, the number is not particularly limited, but 1 to 3 is preferred. The number of ring members of the above aromatic ring group is preferably 5 to 18, more preferably 5 to 12, and even more preferably 5 to 10. Specific examples of aromatic hydrocarbon rings are as described above, but among aromatic hydrocarbon groups, phenyl groups or naphthyl groups are preferred, and phenyl groups are more preferred. Examples of heteroatoms in an aromatic heterocycle include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen atoms being preferred. As mentioned above, specific examples of aromatic heterocyclic groups are as described above, but among aromatic heterocyclic groups, thiophene ring groups, furan ring groups, benzothiophene ring groups, benzofuran ring groups, or pyridine ring groups are preferred.

[0041] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred.

[0042] -SiR Ｓｉ ３ In the base represented by R Ｓｉ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group.

[0043] The above aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the above aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The number of carbon atoms in a linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, and particularly preferably 1 or 2. The number of carbon atoms in a branched aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in a cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 6.

[0044] The above aliphatic heterocyclic group may be monocyclic or polycyclic, with monocyclic being preferred. The number of ring member atoms of the above aliphatic heterocyclic group is preferably 3 to 18, more preferably 5 to 10, and even more preferably 5 to 8. Examples of heteroatoms that the above aliphatic heterocyclic group may have include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur or oxygen atoms being preferred. The definition and specific examples of the above aliphatic heterocyclic group are as described above, with thiolane rings, tetrahydrofuran rings, or tetrahydropyran rings being preferred. As described above, the aliphatic heterocyclic group may have substituents. If the aliphatic heterocyclic group has substituents, the number is not particularly limited, but 1 to 3 is preferred.

[0045] The hydrocarbon group of the acyl group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The number of carbon atoms in the acyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[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, even more preferably 1 to 5, and particularly preferably 1 to 3.

[0047] In equations (2-2) to (2-3), (3-1), and (4-1), X is independently a sulfur atom, an oxygen atom, and -NR Ｘ１ -, -SiR Ｘ２ ２ -, selenium atom, -GeR Ｘ３ ２ -, -CR Ｘ４ ２ -, or -C (=CR) Ｘ５ ２ ) represents -. In formulas (2-2) and (2-3), X is a sulfur atom, an oxygen atom, -NR Ｘ１ -, or a selenium atom is preferred, a sulfur atom or an oxygen atom is more preferred, and a sulfur atom is even more preferred. In formulas (3-1) and (4-1), X is a sulfur atom, an oxygen atom, -NR Ｘ１ -, -SiR Ｘ２ ２ - or -CR Ｘ４ ２ - Preferably a sulfur atom, an oxygen atom, -NR Ｘ１ -, -SiR Ｘ２ ２ - or -CR Ｘ４ ２ - is more preferably a sulfur atom, an oxygen atom, or -CR Ｘ４ ２ - is even more preferable.

[0048] R Ｘ１ ~R Ｘ５ Each of these independently represents a hydrogen atom or a substituent. Examples of the substituents include those exemplified by substituent W described above, with specific substituents being preferred, an aliphatic hydrocarbon group which may have specific substituents, an aromatic ring group which may have specific substituents, or an aliphatic heterocyclic group which may have specific substituents being more preferred, and an aliphatic hydrocarbon group which may have specific substituents or an aromatic ring group which may have specific substituents being even more preferred. Ｘ１ ~R Ｘ５ The definitions and preferred embodiments of an aliphatic hydrocarbon group which may have specific substituents, an aromatic ring group which may have specific substituents, and an aliphatic heterocyclic group which may have specific substituents are the same as those of each group exemplified as specific substituents.

[0049] In Formula (3-4), Formula (3-5), Formula (4-4), and Formula (4-5), Y is independently an oxygen atom, a sulfur atom, or -NR Ｙ１ -. As Y, an oxygen atom is preferred. R Ｙ１ represents a hydrogen atom or a substituent. As R Ｙ１ , a substituent is preferred, and specific examples and preferred embodiments of the substituent represented by R Ｙ１ are the same as those of the substituent represented by R Ｘ１ to R Ｘ５ described above. In Formula (3-4), Formula (3-5), Formula (4-4), and Formula (4-5), R independently represents a hydrogen atom or a substituent. As R, a substituent is preferred, and specific examples and preferred embodiments of the substituent represented by R are the same as those of the substituent represented by R Ｘ１ to R Ｘ５ described above.

[0050] In Formula (5), R Ｘ independently represents a hydrogen atom or a substituent. When all of R Ｘ are the above substituents, R Ｘ may be bonded to each other to form a ring. As the above ring, an aliphatic hydrocarbon ring is preferred. Further, the ring may have a substituent. As R Ｘ , a substituent is preferred, and specific examples and preferred embodiments of the substituent represented by R Ｘ are the same as those of the substituent represented by R Ｘ１ to R Ｘ５ described above. R Ｚ２ represents a hydrogen atom or a substituent. Specific examples and preferred embodiments of the substituent represented by R Ｚ２ are the same as those of the substituent represented by R Ｚ１ described above. A represents a group represented by Formula (A-1). The group represented by Formula (A-1) will be described later.

[0051] As described above, R ＸThese elements may bond to each other to form a ring. The ring may be either an aromatic ring or an aliphatic ring, with an aliphatic ring being preferred. As mentioned above, an aliphatic hydrocarbon ring is particularly preferred as the ring. The ring may be either a monocyclic or polycyclic ring. The number of ring member atoms in the ring is preferably 3 to 20, more preferably 5 to 12, and even more preferably 5 to 10. The ring may have a heteroatom. The heteroatom is preferably a sulfur atom, a nitrogen atom, or an oxygen atom. The substituent that the ring may have is the substituent W mentioned above, and is preferably an alkyl group, an aryl group, or a halogen atom.

[0052] In terms of achieving superior effects of the present invention, the compound represented by formula (1-1) preferably satisfies at least one of requirements A and D, and more preferably satisfies requirement A. Furthermore, the compound represented by formula (1-2) preferably satisfies at least one of requirements A, B, and D, and more preferably satisfies requirement A. Furthermore, the compound represented by formula (1-3) preferably satisfies at least one of requirements A to D, and more preferably satisfies requirement A.

[0053] (Requirement A):C Ａ However, at least one of the four Zs is -CR Ｚ３ The ring represented by equation (2-1) =, where at least one of the two Zs is -CR Ｚ３ The ring represented by equation (2-2) =, or at least one of the two Zs is -CR Ｚ３ The ring is represented by equation (2-3) where equality is given. Ｚ３ This is a base represented by formula (Z). (Requirement B): C Ｂ１ However, at least one of the two Zs is -CR Ｚ３ The ring represented by equation (3-2) =, or at least one of the two Zs is -CR Ｚ３ The ring is represented by the equation (3-3) where equality is given. Ｚ３ This is a base represented by formula (Z). (Requirement C): C Ｂ２ However, at least one of the two Zs is -CR Ｚ３The ring represented by equation (4-2) =, or at least one of the two Zs is -CR Ｚ３ The ring is represented by equation (4-3) where equality is given. Ｚ３ is a base represented by formula (Z). (Requirement D): R in formula (5) Ｚ２ However, this is the base represented by equation (Z).

[0054]

[0055] In formula (Z), Ar represents an aromatic ring group which may have the above-mentioned specific substituents. Specific examples and preferred embodiments of the specific substituents are as described above. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. If the aromatic ring group has substituents, the number is not particularly limited, but 1 to 3 is preferred. The above aromatic ring group may be monocyclic or polycyclic, with monocyclic being preferred. The number of ring members of the above aromatic ring group is preferably 5 to 18, more preferably 5 to 12, and even more preferably 5 to 10. The definition and specific examples of the above 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 that the above aromatic heterocyclic group may have 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 described above are as stated above, and thiophene ring groups, furan ring groups, benzothiophene ring groups, benzofuran ring groups, or pyridine ring groups are preferred. L represents a single bond, a divalent linking group represented by formula (L), or an ethynylene group. R １ and R ２ Each of these independently represents a hydrogen atom or the specific substituent mentioned above. １ and R ２ In all cases, hydrogen atoms are preferred.

[0056] The base represented by formula (A-1) will be described in detail below.

[0057]

[0058] In formula (A-1), C １ This represents a ring containing at least two carbon atoms, which may have substituents.１ The two carbon atoms included are the two carbon atoms explicitly shown in formula (A-1). The number of carbon atoms in the above 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 above ring is the number including the two carbon atoms explicitly shown in the formula. The above ring may be either an aromatic ring or a non-aromatic ring. The above ring may be either a monocyclic or polycyclic ring, and 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 is preferred. 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 above ring may have heteroatoms. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with sulfur, nitrogen, or oxygen being preferred. The number of heteroatoms in the above ring is preferably 0 to 10, and more preferably 0 to 5. １ Of the carbon atoms constituting the ring represented by the formula (A-1), carbon atoms other than those at the bond positions marked with an asterisk (*) in formula (A-1) and the carbon atoms bonded to Q may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S).

[0059] The above CC １ Examples of substituents that the ring represented by may have include the groups exemplified by substituent W above, and are preferably halogen atoms, alkyl groups, aromatic ring groups, cyano groups, or silyl groups, with halogen atoms or alkyl groups being more preferred. The alkyl group may be linear, branched, or cyclic, with linear being preferred. The alkyl group has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0060] The above CC １The rings represented by are preferably rings used as acidic nuclei (for example, acidic nuclei of merocyanine dyes), and examples of nuclei include the following: (a) 1,3-dicarbonyl nuclei: for example, 1,3-indanedione nuclei, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione. (b) Pyrazolinone nuclei: 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 nuclei: for example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one. (d) Oxindole nuclei: for example, 1-alkyl-2,3-dihydro-2-oxindole. (e) 2,4,6-trioxohexahydropyrimidine core: for example, barbituric acid, 2-thiobarbituric acid, and its derivatives. Examples of the above 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 core: for example, rhodanine and its derivatives. Examples of the above 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 core (2-thio-2,4-(3H,5H)-oxazoledione core): For example, 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone core: For example, 3(2H)-thianaphthenone-1,1-dioxide. (i) 2-thio-2,5-thiazolidinedione core: For example, 3-ethyl-2-thio-2,5-thiazolidinedione.(j) 2,4-thiazolidinedione nuclei: e.g., 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione, etc. (k) thiazolin-4-one nuclei: e.g., 4-thiazolinone and 2-ethyl-4-thiazolinone, etc. (l) 2,4-imidazolidinedione (hydantoin) nuclei: e.g., 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione, etc. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nuclei: e.g., 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione, etc. (n) Imidazolin-5-one core: e.g., 2-propylmercapto-2-imidazolin-5-one. (o) 3,5-pyrazolidinedione core: e.g., 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione. (p) Benzothiophen-3(2H)-one core: e.g., benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one. (q) Indanone core: e.g., 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone. (r) Benzofuran-3-(2H)-one nucleus: e.g., benzofuran-3-(2H)-one. (s) 2,2-dihydrophenalen-1,3-dione nucleus, etc.

[0061] In equation (A-1), Q is an oxygen atom, a sulfur atom, =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ This represents Q, where an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred, in terms of superior effects of the present invention. Ｑ１ R represents a hydrogen atom or a substituent. Examples of substituents include the group exemplified by substituent W above. Ｑ２ and R Ｑ３ These are, independently, a cyano group and -SO ２ R Ｑ４ , -COOR Ｑ５ , -COR Ｑ６ , or -S(=O)RＱ７ Represents R Ｑ４ ~R Ｑ７ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. The definition of an aliphatic hydrocarbon group is as described above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The definition of an aromatic ring group is as described above, and an aromatic hydrocarbon group is preferred, with a phenyl group being more preferred. The definition of an aliphatic heterocyclic group is as described above, and the heteroatom of the above aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. Ｑ４ ~R Ｑ７ Examples of substituents that each group represented by the above substituent W may have include the substituents exemplified by substituent W. * indicates a bond position.

[0062] The group represented by formula (A-1) is preferably the group represented by formula (A-2) in that the effects of the present invention are superior.

[0063]

[0064] In formula (A-2), C ２ This represents a ring containing at least three carbon atoms, which may have substituents. ２The three carbon atoms included are the three carbon atoms explicitly shown in formula (A-2). The number of carbon atoms in the above 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 above ring is the number including the three carbon atoms explicitly shown in the formula. The above ring may be either an aromatic ring or a non-aromatic ring. The above ring may be either a monocyclic or polycyclic ring, and a fused ring containing a 5-membered ring, a 6-membered ring, or at least one of a 5-membered ring and a 6-membered ring is preferred. 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 above ring may have heteroatoms. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with sulfur, nitrogen, or oxygen being preferred. The number of heteroatoms in the above ring is preferably 0 to 10, and more preferably 0 to 5. ２ Among the carbon atoms constituting the ring represented by the formula (A-2), the carbon atoms at the bond positions marked with *, and Q ２ and Q ３ A preferred embodiment of the substituents that the above ring may have is the above-mentioned ring C １ This is similar to the substituents that may be present.

[0065] In formula (A-2), Q ２ and Q ３ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ ~R Ｑ３ As stated above. Q ２ and Q ３ In terms of superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0066] In terms of achieving superior effects of the present invention, it is preferable that A in formula (5) is a group represented by formula (C-1) or a group represented by formula (C-2).

[0067]

[0068] In formula (C-1), X ｃ１ and X ｃ２ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ ~R Ｑ３ These are R in the above formula (A-1), respectively. Ｑ１ ~R Ｑ３ This is synonymous with X. ｃ１ and X ｃ２ In terms of superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. ３ represents an aromatic ring which may have substituents. The aromatic ring may be monocyclic or polycyclic. The number of member atoms of the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of member atoms of the aromatic ring is the number including the two carbon atoms explicitly shown in the formula. Furthermore, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. ３ The aromatic ring represented by is as described above, and is preferably a benzene ring, naphthalene ring, anthracene ring, pyrene ring, thiophene ring, furan ring, thiazole ring, oxazole ring, pyridine ring, thienothiophene cyclic ring, benzothiophene ring, benzofuran ring, pyrazine ring, pyrimidine ring, or pyridazine ring, more preferably a benzene ring, naphthalene ring, or thiophene ring, and even more preferably a benzene ring. Examples of substituents that the aromatic ring may have are the groups exemplified by substituent W, and alkyl groups or halogen atoms are 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.

[0069] In formula (C-2), X ｃ３ ~X ｃ５ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ ~RＱ３ These are R in the above formula (A-1), respectively. Ｑ１ ~R Ｑ３ This is synonymous with X. ｃ３ ~X ｃ５ In terms of superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. ｃ１ and Z ｃ２ Each of these is independently -NR ｃ１ - or -CR ｃ２ ２ - indicates that the effects of the present invention are superior, and -NR ｃ１ - is preferable. R ｃ１ and R ｃ２ Each independently represents a hydrogen atom or a substituent. Examples of the substituent include the group exemplified by substituent W, and alkyl groups or aryl groups are preferred, with alkyl groups being more preferred. The alkyl group may be linear, branched, or cyclic, with linear being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 20, 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 phenyl groups being preferred. The aryl group may have further substituents, and examples of substituents include the group exemplified by substituent W.

[0070] The following are specific examples of particular compounds, but the present invention is not limited to these.

[0071]

[0072]

[0073]

[0074]

[0075] Specific examples of the group represented by A are shown below. Note that Ph represents a phenyl group and Me represents a methyl group.

[0076]

[0077]

[0078]

[0079] The molecular weight of the specific compound is preferably 400 to 1000, more preferably 400 to 800, and even more preferably 400 to 700. It is presumed that when the molecular weight is as described above, the sublimation temperature of the specific compound will be lower, resulting in excellent manufacturability.

[0080] The specific compound is preferably one with a single-film ionization potential of -5.0 to -6.5 eV, in terms of stability when used as a p-type organic semiconductor and energy level matching with an n-type organic semiconductor.

[0081] The maximum absorption wavelength of the specific compound is preferably in the range of 400 to 650 nm, and more preferably in the range of 400 to 600 nm. The above maximum absorption wavelength is the value measured in solution (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 does not dissolve in chloroform, the maximum absorption wavelength of the specific compound is determined by measuring the value obtained using the specific compound in the form of a film after deposition.

[0082] The specific compound is particularly useful as a material for photoelectric conversion films used in image sensors, optical sensors, or photocells. The specific compound often functions as a dye within the photoelectric conversion film. Furthermore, the specific compound can also be used as a coloring material, liquid crystal material, organic semiconductor material, charge transport material, pharmaceutical material, and fluorescent diagnostic agent material.

[0083] The specific compound may be purified as needed. Examples of purification methods for the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, slurry washing, reprecipitation purification, purification using adsorbents such as activated carbon, and recrystallization purification.

[0084] The content of the specific compound in the photoelectric conversion film (= film thickness of the specific compound on a single-layer basis / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75 volume%, more preferably 10 to 50 volume%, and even more preferably 15 to 40 volume%. Only one specific compound may be used, or two or more may be used. When two or more are used, it is preferable that their total amount is within the above range.

[0085] <n-type organic semiconductor> The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the specified compounds mentioned above. The n-type organic semiconductor is a compound different from the specified compounds mentioned above. The n-type organic semiconductor is an acceptor organic semiconductor material (compound), and refers to an organic compound that has the property of readily accepting electrons. In other words, the n-type organic semiconductor is the organic compound with the greater electron affinity when two organic compounds are used in contact. In other words, any organic compound that has electron-accepting properties can be used as an acceptor organic semiconductor. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and their derivatives; condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives); and heterocyclic compounds of 5 to 7 membered rings having at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, etc.). ); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid diimide derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and their derivatives; triazole compounds; distylyl arylene derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silole compounds; 3,4,9,10-perylenetetracarboxylic acid dianhydride; 3,4,9,10-perylenetetracarboxylic acid diimide derivatives; and the compounds described in paragraphs

[0056] to

[0057] of Japanese Patent Application Publication No. 2006-100767.

[0086] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and their derivatives are preferred. For example, fullerene C６０ , 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 Examples include , and mixed fullerenes. Fullerene derivatives include, for example, compounds obtained by adding substituents to the above fullerene. Preferred substituents are alkyl groups, aryl groups, or heterocyclic groups. As fullerene derivatives, compounds described in Japanese Patent Application Publication No. 2007-123707 are preferred.

[0087] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.

[0088] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or in the range of 400 to 600 nm.

[0089] 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 the specific compound and the n-type organic semiconductor are mixed and dispersed. The photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs

[0013] to

[0014] of Japanese Patent Application Publication No. 2005-303266.

[0090] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or greater.

[0091] The n-type organic semiconductor may be used alone or in combination of two or more types. When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (film thickness of the n-type organic semiconductor on a single-layer basis / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 20 to 50 volume%.

[0092] When the n-type organic semiconductor contains fullerenes, the content of fullerenes relative to the total content of the n-type organic semiconductor (film thickness of fullerenes on a single-layer basis / total film thickness of each n-type organic semiconductor on a single-layer basis × 100) is preferably 50 to 100 volume%, and more preferably 80 to 100 volume%. Fullerenes may be used individually or in combination of two or more types.

[0093] 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 of the specific compound on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the n-type organic semiconductor on a single-layer basis) × 100) is preferably 20 to 80 volume%, and more preferably 40 to 80 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 of the specific compound on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the n-type organic semiconductor on a single-layer basis + film thickness of the p-type organic semiconductor on a single-layer basis) × 100) is preferably 10 to 75 volume%, and more preferably 15 to 50 volume%. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, an n-type organic semiconductor, and a p-type organic semiconductor included as desired. "Substantial" 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.

[0094] <p-type organic semiconductor> The photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the specified compounds mentioned above. The p-type organic semiconductor is a compound different from the specified compounds mentioned above. A p-type organic semiconductor is a donor organic semiconductor material (compound), which is an organic compound that readily donates electrons. In other words, a p-type organic semiconductor is the organic compound with the smaller ionization potential when two organic compounds are brought into contact. A single p-type organic semiconductor may be used, or two or more may be used.

[0095] Examples of p-type organic semiconductors include triarylamine compounds (for example, 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 Japanese Patent Application Publication No. 2011-228614, compounds described in paragraphs

[0052] to

[0063] of Japanese Patent Application Publication No. 2011-176259, and compounds described in paragraphs

[0119] to

[0158] of Japanese Patent Application Publication No. 2011-225544) Compounds, compounds described in paragraphs

[0044] to

[0051] of Japanese Patent Publication No. 2015-153910, and compounds described in paragraphs

[0086] to

[0090] of Japanese Patent Publication 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 JP 2018-014474, compounds described in paragraphs

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

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

[0015] to

[0025] of WO2018 / 207722, and the compounds described in paragraph

[00] of JP 2019-054228. Compounds described in paragraphs

[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 JP 2019-80052, 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 JP 2019-050398,The compounds described in paragraphs

[0033] to

[0036] of Japanese Patent Publication No. 2018-206878, the compounds described in paragraph

[0038] of Japanese Patent Publication No. 2018-190755, the compounds described in paragraphs

[0019] to

[0021] of Japanese Patent Publication No. 2018-026559, the compounds described in paragraphs

[0031] to

[0056] of Japanese Patent Publication No. 2018-170487, the compounds described in paragraphs

[0036] to

[0041] of Japanese Patent Publication No. 2018-078270, and Japanese Patent Publication No. 2018-166200 The compounds described in paragraphs

[0055] to

[0082] of the Patent Publication No. 2018-113425, the compounds described in paragraphs

[0041] to

[0050] of the Patent Publication No. 2018-085430, the compounds described in paragraphs

[0044] to

[0048] of the Patent Publication No. 2018-056546, the compounds described in paragraphs

[0041] to

[0045] of the Patent Publication No. 2018-046267, and paragraphs

[0042] to

[0049] of the Patent Publication No. 2018-014474 Examples include compounds described in

[0031] to

[0036] , compounds described in paragraphs

[0036] to

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

[0045] to

[0048] of Japanese Patent Application Publication No. 2020-010024, etc.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives, etc.), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, aminosubstituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having nitrogen-containing heterocyclic compounds as ligands. Furthermore, as p-type organic semiconductors, benzoxazole compounds (for example, the compounds described in Figures 3 to 7 of Japanese Patent Publication No. 2022-123944), dicarbazole compounds (for example, the compounds described in Figures 2 to 5 of Japanese Patent Publication No. 2022-122839), benzoquinazoline compounds (for example, the compounds described in paragraphs

[0053] to

[0056] of Japanese Patent Publication No. 2022-120323),Azine compounds (for example, compounds described in paragraphs

[0041] to

[0042] of Japanese Patent Publication No. 2022-120273), compounds described in Figures 2 to 10 of Japanese Patent Publication No. 2022-115832, indrotriphenylene compounds (for example, compounds described in paragraphs

[0065] to

[0072] of Japanese Patent Publication No. 2022-108268), indrocarbazole compounds (for example, paragraphs

[0052] to [00 Examples of p-type organic semiconductors include compounds described in paragraph

[0028] of Japanese Patent Publication No. 2022-100258, triscarbazolylphenyl compounds (for example, compounds described in paragraphs

[0038] to

[0040] of Japanese Patent Publication No. 2022-181226), compounds described in paragraphs

[0070] to

[0082] of Japanese Patent Publication No. 2022-027575, and compounds described in paragraphs

[0051] to

[0064] of Japanese Patent Publication No. 2021-163968. Examples of p-type organic semiconductors include compounds with a smaller ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductors are given below.

[0096]

[0097]

[0098]

[0099]

[0100] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or greater.

[0101] The p-type organic semiconductor may be used alone or in combination of two or more types. When the photoelectric conversion film contains a p-type organic semiconductor, the p-type organic semiconductor content in the photoelectric conversion film (film thickness of the p-type organic semiconductor on a single-layer basis / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 25 to 50 volume%.

[0102] Photoelectric conversion films containing specific compounds are non-luminescent films and have characteristics different from organic light-emitting diodes (OLEDs). A non-luminescent film is defined as a film with a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less. The lower limit is often 0% or more.

[0103] <Dyes> The photoelectric conversion film preferably contains a dye in addition to the specified compounds mentioned above. The dye is a compound different from the specified compounds mentioned above. Organic dyes are preferred as dyes. Examples of organic dyes 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, azametine dyes, coumarin dyes, allylidene 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 Examples of organic dyes include cridinone 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 WO2020 / 013246, WO2022 / 168856, Japanese Patent Publication No. 2023-10305, and Japanese Patent Publication No. 2023-10299, as well as acceptor-donor-acceptor type dyes in which two acidic nuclei are bound to a donor, and donor-acceptor-donor type dyes in which two donors are bound to an acceptor. Among organic dyes, cyanine dyes, imidazoquinoxaline dyes, acceptor-donor-acceptor type dyes, and donor-acceptor type dyes are preferred.

[0104] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the range of 400 to 650 nm, and even more preferably in the range of 450 to 650 nm.

[0105] The dye may be used alone or in combination of two or more types. The amount of dye in the photoelectric conversion film relative to the total amount of the specific compound and the dye (= (film thickness of the dye on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the dye on a single-layer basis) × 100)) is preferably 5 to 75 volume%, more preferably 5 to 60 volume%, and even more preferably 5 to 50 volume%.

[0106] <Method of Film Formation> As a method for forming the above-mentioned photoelectric conversion film, for example, a dry film formation method can be used. Examples of dry film formation methods include vapor deposition (especially vacuum deposition), sputtering, ion plating, and physical vapor deposition methods such as MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, with vacuum deposition being preferred. When forming a photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0107] The film thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm.

[0108] [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 from the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Being transparent to the light to be detected means that the average transmittance of light in the wavelength range to be detected is 50% or more, preferably 60% or more, and more preferably 70% or more. Specifically, it is preferable that it be transparent to light with a wavelength of 400 to 800 nm. The above transmittance can be measured using a spectrophotometer. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, as well as nanocarbon materials such as carbon nanotubes and graphene. Conductive metal oxides are preferred in terms of high conductivity and transparency.

[0109] Typically, when a conductive film is made thinner than a certain range, its resistance often increases sharply. In the solid-state image sensor incorporating the photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10000 Ω / □, and there is a great degree of freedom in the range of film thickness that can be thinned. Also, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the light transmittance increases. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and increases the photoelectric conversion ability. Considering the suppression of leakage current, the increase in the resistance of the thin film, and the increase in transmittance associated with thinning, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0110] The lower electrode 11 may be made transparent or opaque to reflect light, depending on the application. The definition of transparency in the lower electrode 11 is the same as that for the upper electrode 15 described above. Examples of materials that make up the lower electrode 11 include conductive metal oxides such as antimony or fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium 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.

[0111] The method for forming electrodes can be appropriately selected depending on the electrode material. Specifically, 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 (sol-gel method, etc.), and coating of indium tin oxide dispersions.

[0112] [Charge-blocking films: electron-blocking films, hole-blocking films] It is preferable that the photoelectric conversion element has one or more intermediate layers between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film. An example of the above intermediate layer is a charge-blocking film. When the photoelectric conversion element has this film, the characteristics of the resulting photoelectric conversion element (quantum efficiency, response speed, etc.) are better. Examples of charge-blocking films include electron-blocking films and hole-blocking films.

[0113] <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 electron blocking films. Examples of polymer materials include polymers such as phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, as well as their derivatives.

[0114] Furthermore, the electron blocking film may be composed of multiple films. The electron blocking film may also be composed of inorganic materials. Generally, inorganic materials have a higher dielectric constant than organic materials, so when inorganic materials are 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 as electron blocking films 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.

[0115] <Hole Blocking Film> The hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type organic semiconductor can be used. The hole blocking film may also be composed of multiple films.

[0116] Examples of methods for manufacturing charge-blocking films include dry deposition and wet deposition. Examples of dry deposition methods include vapor deposition and sputtering. Vapor deposition can be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition methods such as vacuum deposition being preferred. Examples of wet deposition methods include inkjet, spray, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with inkjet being preferred in terms of high-precision patterning.

[0117] The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.

[0118] [Substrate] The photoelectric conversion element may further have a substrate. Examples of substrates include semiconductor substrates, glass substrates, and plastic substrates. Typically, the substrates are layered on the substrate in the following order: conductive film, photoelectric conversion film, and transparent conductive film.

[0119] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. Photoelectric conversion materials can be significantly degraded in performance due to the presence of degradation factors such as water molecules. Therefore, the entire photoelectric conversion film can be sealed by covering it with a sealing layer made of a dense metal oxide, metal nitride or metal nitride oxide ceramic, or diamond-like carbon (DLC), which does not allow water molecules to penetrate, thereby preventing the above-mentioned degradation. Examples of sealing layers include those described in paragraphs

[0210] to

[0215] of Japanese Patent Application Publication No. 2011-082508, and these contents are incorporated herein by reference.

[0120] [Method for Manufacturing a Photoelectric Conversion Element] Known manufacturing methods can be used to manufacture a photoelectric conversion element. Specifically, for example, a method for manufacturing a photoelectric conversion element can be used that includes the steps of forming a conductive film on a substrate, forming a photoelectric conversion film, and forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may also include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer). The method for forming each layer is as described above.

[0121] [Image Sensor] One example of an application of photoelectric conversion elements is an image sensor. An image sensor is an element that converts the optical information of an image into an electrical signal. Typically, multiple photoelectric conversion elements are arranged in a matrix on the same plane, and each photoelectric conversion element (pixel) converts the optical signal into an electrical signal, and these electrical signals can be output sequentially to the outside of the image sensor for each pixel. For this purpose, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The method of manufacturing an image sensor is not particularly limited, but one example is a method that includes the process of manufacturing the photoelectric conversion elements described above.

[0122] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, photocells and optical sensors, 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 it may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line or as a two-dimensional sensor arranged on a plane.

[0123] [Compounds] This invention also includes inventions of specific compounds.

[0124] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0125] [Compounds used in photoelectric conversion films] The following lists the materials used in the photoelectric conversion films.

[0126] [Synthesis of Compound (D-1)] Compound (D-1) can be synthesized according to the following scheme. The compounds used in the examples and comparative examples other than compound (D-1) for the photoelectric conversion film are synthesized in accordance with the synthesis method of compound (D-1).

[0127]

[0128] (Synthesis of compound (D-1-2)) Compound (D-1-2) can be synthesized, for example, by reacting compound (D-1-1) and sodium borohydride in methanol at room temperature.

[0129] (Synthesis of compound (D-1-3)) Compound (D-1-3) can be obtained, for example, by reacting compound (D-1-2) obtained in the above procedure in toluene in the presence of p-toluenesulfonic acid under heating reflux.

[0130] (Synthesis of compound (D-1-4)) Compound (D-1-4) can be obtained, for example, by reacting compound (D-1-3) obtained in the above procedure with dichloromethyl methyl ether in dichloromethane at room temperature in the presence of tin(IV) chloride and 2,6-dibromopyridine.

[0131] (Synthesis of compound (D-1-5)) Compound (D-1-5) can be obtained, for example, by reacting compound (D-1-4) obtained in the above procedure with benzofuran-2-boronic acid in a tetrahydrofuran (THF)-water mixed solvent at 60°C in the presence of (2-dicyclohexylphosphin-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (XPhos Pd G3) as a metal catalyst and tripotassium phosphate as a base.

[0132] (Synthesis of compound (D-1)) Compound (D-1) can be obtained, for example, by reacting compound (D-1-5) obtained in the above procedure with 1,3-indanedione in the presence of piperidine in toluene at 100°C.

[0133] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for the comparative examples are shown below. Compounds (C-1) to (C-3) are comparative compounds, while the other compounds are specific compounds.

[0134]

[0135]

[0136]

[0137] [n-type organic semiconductor] ・C ６０ : Fullerene (C ６０ )

[0138] [p-type organic semiconductor]

[0139]

[0140] [Pigment]

[0141]

[0142] [Evaluation] A photoelectric conversion element will be fabricated using the above materials, and the following tests X and Y will be performed.

[0143] [Test X] A photoelectric conversion element will be fabricated as described below, and the quantum efficiency, response speed, and electric field strength dependence of the quantum efficiency when the photoelectric conversion element receives blue-green light (wavelength 450 nm) will be evaluated using the following method.

[0144] <Fabrication of Photoelectric Conversion Element> A photoelectric conversion element in the form shown in Figure 2 is fabricated using the various components shown above. Here, the photoelectric conversion element consists of 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 is deposited on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and then a compound (EB-1) is deposited on the lower electrode 11 by vacuum heating deposition to form the electron blocking film 16A (thickness: 30 nm). Subsequently, with the glass substrate at room temperature, each specific compound or each comparative compound shown in Table 1 and an n-type organic semiconductor (fullerene (C)) are deposited on the electron blocking film 16A. ６０ A p-type organic semiconductor (compound P-1) and a photoelectron ion (ITO) are co-deposited by vacuum deposition to form a film with a single-layer thickness of 80 nm for each. This forms a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. The deposition rate of the photoelectric conversion film 12 is set to 1.0 Å / sec. Further, compound (EB-2) is deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO is deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming an SiO film as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al) is deposited thereon by ALCVD (Atomic Layer Chemical Vapor Deposition). ２ O３ A layer is formed, and the resulting laminate is 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 obtained photoelectric conversion element is measured using the following method. 2.5 × 10⁻¹⁰ ₀ ５ A voltage is applied to achieve an electric field strength of V / cm, and the current value in the dark (dark current) is measured. As a result, the dark current for all photoelectric conversion elements was 50 nA / cm. ２ The following confirms that it exhibits a sufficiently low dark current.

[0147] <Quantum Efficiency> For each photoelectric conversion element, the quantum efficiency when receiving blue-green light is measured using the following method. 2.0 × 10⁻¹⁶ for each photoelectric conversion element. ５ After applying a voltage to achieve an electric field strength of V / cm, light is irradiated from the upper electrode (transparent conductive film) side, and the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 450 nm is evaluated. The photoelectric conversion efficiency of each photoelectric conversion element (= (photoelectric conversion efficiency of each photoelectric conversion element) / (photoelectric conversion efficiency of the photoelectric conversion element of Example 1-1)) is calculated with the photoelectric conversion efficiency of Example 1-1 set to 1, and the quantum efficiency is evaluated from the obtained value according to the evaluation criteria below. A quantum efficiency of C or higher is preferable.

[0148] A: Quantum efficiency (relative ratio) of 0.95 or higher B: Quantum efficiency (relative ratio) of 0.80 or higher and less than 0.95 C: Quantum efficiency (relative ratio) of 0.70 or higher and less than 0.80 D: Quantum efficiency (relative ratio) less than 0.70

[0149] <Response Speed> The response speed of each photoelectric conversion element when exposed to blue-green light is evaluated using the following method. 2.0 × 10⁻¹⁶ ５A voltage is applied to achieve an intensity of V / cm. Then, the LED (light emitting diode) is momentarily lit to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 450 nm at that time is measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. The rise time of each photoelectric conversion element is determined by setting the above rise time of the photoelectric conversion element of Example 1-1 as 1 (= (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element of Example 1-1)), and the response speed is evaluated according to the evaluation criteria below. A response speed of C or higher is preferable.

[0150] A: Relative response time less than 1.1 B: Relative response time 1.1 or higher, less than 1.5 C: Relative response time 1.5 or higher, less than 2.0 D: Relative response time 2.0 or higher

[0151] <Dependence of quantum efficiency on electric field strength> For each photoelectric conversion element, the dependence of the quantum efficiency on electric field strength when exposed to blue-green light is evaluated using the following method. In the evaluation of <quantum efficiency> above, the voltage applied to each photoelectric conversion element is 5.0 × 10 ４ Except for changing to V / cm, the procedure was the same: 5.0 × 10 ４ The quantum efficiency (photoelectric conversion efficiency) at V / cm is measured. The electric field strength dependence of the quantum efficiency is calculated according to equation (S1), and the electric field strength dependence of the quantum efficiency is evaluated according to the evaluation criteria below. An evaluation of C or higher for the electric field strength dependence of the quantum efficiency is preferable. In equation (S1), the numerator and denominator are the values ​​measured for the photoelectric conversion element of the same example or comparative example. For example, for Example 1-1, the electric field strength at a wavelength of 450 nm of the photoelectric conversion element of Example 1-1 is 5.0 × 10⁻¹⁰. ４ Photoelectric conversion efficiency at V / cm and electric field strength of 2.0 × 10⁻¹⁰ at a wavelength of 450 nm for the photoelectric conversion element of Example 1-1. ５ This is compared with the photoelectric conversion efficiency at V / cm. Equation (S1): Dependence of quantum efficiency on electric field strength = (Applied voltage to each photoelectric conversion element 5.0 × 10⁻⁶) ４ (Photoelectric conversion efficiency at V / cm) / (Applied voltage to each photoelectric conversion element 2.0 × 10⁻¹⁰) ５Photoelectric conversion efficiency in V / cm)

[0152] A: The electric field strength dependence of quantum efficiency is 0.90 or higher. B: The electric field strength dependence of quantum efficiency is 0.85 or higher and less than 0.90. C: The electric field strength dependence of quantum efficiency is 0.80 or higher and less than 0.85. D: The electric field strength dependence of quantum efficiency is less than 0.80.

[0153] [Results (Test X)]

[0154] The evaluation results are shown in Table 1 below. In the table, the column "A = Formula (C-1), (C-2)" is set to "A" if A in formula (5) is the group represented by formula (C-1) or formula (C-2), and to "B" otherwise. Ｚ１ , R Ｚ２ In the "=Formula (Z)" column, "A" is used if the specific compound satisfies at least one of requirements A to D, and "B" otherwise. In the table, in the "Compound = Formula (1-1)" column, "A" is used if the specific compound is a compound represented by formula (1-1), and "B" otherwise. In the table, "C Ａ The column "=Equation (2-1)" is C in equations (1-1) to (1-3). Ａ However, if the ring is represented by equation (2-1), it is designated as "A," and in all other cases, it is designated as "B."

[0155]

[0156] The results shown in Table 1 demonstrate that the photoelectric conversion element of the present invention exhibits low dependence of quantum efficiency on electric field strength when receiving blue-green light. Furthermore, the photoelectric conversion element of the present invention is shown to exhibit excellent quantum efficiency and response speed when receiving blue-green light.

[0157] From a comparison of Examples 1-1 to 1-10, it is shown that when A in formula (5) is a group represented by formula (C-1) or a group represented by formula (C-2), the quantum efficiency and the electric field strength dependence of the quantum efficiency are superior. From a comparison of Examples 1-11 to 1-14 and 1-17 to 1-19, it is shown that when a specific compound satisfies at least one of requirements A to D, the response speed and the electric field strength dependence of the quantum efficiency are superior. From a comparison of Examples 1-1 to 1-8 and 1-11 to 1-14, it is shown that when a specific compound is a compound represented by formula (1-1), the response speed and the electric field strength dependence of the quantum efficiency are superior. From a comparison of Examples 1-1 to 1-8 and 1-15, it is shown that in formulas (1-1) to (1-3), C Ａ However, it is shown that the quantum efficiency is better when the ring is represented by equation (2-1).

[0158] [Test Y] Next, in addition to the specified compound or comparative compound, a photoelectric conversion element is fabricated using the above dyes (R-1) to (R-10) other than the specified compound, and the quantum efficiency, response speed, and electric field strength dependence of the quantum efficiency of the photoelectric conversion element at a wavelength of 450 nm are evaluated by the following method. Each specified compound or each comparative compound, n-type organic semiconductor (fullerene (C ６０ Each photoelectric conversion element is fabricated using the same procedure as in [Test X], except that a photoelectric conversion film 12 (film thickness 320 nm) is formed by co-depositing using a vacuum deposition method with a p-type organic semiconductor (compound P-1) and one of the dyes (R-1) to (R-10) such that the ratio of the specific compound or comparative compound:dye:p-type organic semiconductor:n-type organic semiconductor = 1:1:2:2 on a single-layer basis. When each of the fabricated photoelectric conversion elements was evaluated in [Evaluation X], the same results as those shown in Table 1 were obtained even when a dye other than the specific compound was used in combination. Specifically, for example, a photoelectric conversion element fabricated according to the above method using compound (D-1) as the specific compound and compound (R-1) as the dye other than the specific compound shows quantum efficiency, response speed, and electric field strength dependence of quantum efficiency equivalent to Example 1-1 in Table 1. Photoelectric conversion elements are fabricated and each evaluation is performed for all combinations of each specific compound and each dye.

[0159] 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 any one of formulas (1-1) to (1-3). In formula (1-1), C Ａ represents a ring represented by any one of formulas (2-1) to (2-3). C Ｃ represents a ring represented by formula (5). Incidentally, C Ａ The ring represented by and C Ｃ The ring represented by are fused at the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with * in formula (5). In formula (1-2), C Ａ represents a ring represented by any one of formulas (2-1) to (2-3). C Ｂ１ represents a ring represented by any one of formulas (3-1) to (3-5). C Ｃ represents a ring represented by formula (5). Incidentally, C Ａ The ring represented by and C Ｂ１ The ring represented by are fused at the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with *1 in formulas (3-1) to (3-5). Also, C Ｂ１ The ring represented by and C Ｃ The ring represented by are fused at the position of the carbon atom marked with *2 in formulas (3-1) to (3-5) and the position of the carbon atom marked with * in formula (5). In formula (1-3), C Ａ represents a ring represented by any one of formulas (2-1) to (2-3). C Ｂ１ represents a ring represented by any one of formulas (3-1) to (3-5). C Ｂ２ represents a ring represented by any one of formulas (4-1) to (4-5). C Ｃ represents a ring represented by formula (5). Incidentally, C Ａ The ring represented by and C Ｂ１ The ring represented by are fused at the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with *1 in formulas (3-1) to (3-5). Also, C Ｂ１ The ring represented by and C Ｂ２ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *2 in formulas (3-1) to (3-5) and the position of the carbon atom marked with *2 in formulas (4-1) to (4-5). Ｂ２ A ring represented by C Ｃ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *3 in formulas (4-1) to (4-5) and the position of the carbon atom marked with * in formula (5). In formulas (2-1) to (2-3), formula (3-2), formula (3-3), formula (4-2), and formula (4-3), Z is independently -CR Ｚ１ = or represents a nitrogen atom. R Ｚ１ represents a hydrogen atom or a specific substituent. The specific substituent is -NR Ｎ ２ R represents substituents that do not contain either , or -CH=A. Ｎ Each independently represents a hydrogen atom or a substituent. A represents the group represented by formula (A-1). In formulas (2-2) to (2-3), formula (3-1), and formula (4-1), X independently represents a sulfur atom, an oxygen atom, and -NR Ｘ１ -, -SiR Ｘ２ ２ -, selenium atom, -GeR Ｘ３ ２ -, -CR Ｘ４ ２ -, or -C (=CR) Ｘ５ ２ ) represents R Ｘ１ ~R Ｘ５ Each independently represents a hydrogen atom or a substituent. In formulas (3-4), (3-5), (4-4), and (4-5), Y independently represents an oxygen atom, a sulfur atom, or -NR Ｙ１ Represents -. R Ｙ１ R represents a hydrogen atom or a substituent. In formulas (3-4), (3-5), (4-4), and (4-5), R independently represents a hydrogen atom or a substituent. In formula (5), R Ｘ Each of these independently represents a hydrogen atom or a substituent. Ｘ If all of them are substituents, R Ｘ These elements may join together to form a ring. Ｚ２ represents a hydrogen atom or substituent. A represents a group represented by formula (A-1). In formula (A-1), C １ Q represents a ring containing at least two carbon atoms, which may have substituents. Q represents an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ R represents a hydrogen atom or substituent. Ｑ２ and R Ｑ３ These are, independently, a cyano group and -SO ２ R Ｑ４ , -COOR Ｑ５ , -COR Ｑ６ , or -S(=O)R Ｑ７ Represents R Ｑ４ ~R Ｑ７ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position.

2. The photoelectric conversion element according to claim 1, wherein A in formula (5) is a group represented by formula (C-1) or a group represented by formula (C-2). In formula (C-1), X ｃ１ and X ｃ２ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ ~R Ｑ３ These are R in formula (A-1) above, respectively. Ｑ１ ~R Ｑ３ This is synonymous with C. ３ X represents an aromatic ring which may have substituents. In formula (C-2), X ｃ３ ~X ｃ５ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ ~R Ｑ３ These are R in formula (A-1) above, respectively. Ｑ１ ~R Ｑ３ This is synonymous with Z. ｃ１ and Z ｃ２ Each of these is independently -NR ｃ１ - or -CR ｃ２ ２ Represents -. R ｃ１ and R ｃ２ Each of these independently represents a hydrogen atom or a substituent. * indicates a bond position.

3. The compound represented by the formula (1-1) satisfies at least one of Requirement A and Requirement D, the compound represented by the formula (1-2) satisfies at least one of Requirement A, Requirement B, and Requirement D, and the compound represented by the formula (1-3) satisfies at least one of Requirement A, Requirement B, Requirement C, and Requirement D. The photoelectric conversion element according to claim 1. (Requirement A): C Ａ represents a ring represented by the formula (2-1) in which at least one of the four Zs is -CR Ｚ３ =, a ring represented by the formula (2-2) in which at least one of the two Zs is -CR Ｚ３ =, or a ring represented by the formula (2-3) in which at least one of the two Zs is -CR Ｚ３ =. R Ｚ３ is a group represented by the following formula (Z). (Requirement B): C Ｂ１ represents a ring represented by the formula (3-2) in which at least one of the two Zs is -CR Ｚ３ =, or a ring represented by the formula (3-3) in which at least one of the two Zs is -CR Ｚ３ =. R Ｚ３ is a group represented by the formula (Z). (Requirement C): C Ｂ２ represents a ring represented by the formula (4-2) in which at least one of the two Zs is -CR Ｚ３ =, or a ring represented by the formula (4-3) in which at least one of the two Zs is -CR Ｚ３ =. R Ｚ３ is a group represented by the formula (Z). (Requirement D): R Ｚ２ in the formula (5) is a group represented by the formula (Z). In the formula (Z), Ar represents an aromatic ring group which may have the specific substituent. L represents a single bond, a divalent linking group represented by the formula (L), or an ethynylene group. R １ and R ２ each independently represent a hydrogen atom or the specific substituent. * represents the bonding position.

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

5. In the above formulas (1-1) to (1-3), C Ａ The photoelectric conversion element according to claim 1, wherein the ring is represented by formula (2-1).

6. The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion film further comprises an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed by mixing a compound represented by any one of the formulas (1-1) to (1-3) and the n-type organic semiconductor.

7. The photoelectric conversion element according to claim 6, wherein the n-type organic semiconductor comprises fullerenes selected from the group consisting of fullerenes and their derivatives.

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

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

10. A photoelectric conversion element according to any one of claims 1 to 5, wherein the conductive film and the transparent conductive film are interposed between them, and one or more intermediate layers in addition to the photoelectric conversion film.

11. An image sensor having a photoelectric conversion element according to any one of claims 1 to 5.

12. A light sensor having a photoelectric conversion element according to any one of claims 1 to 5.

13. A method for manufacturing an image sensor, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 5.

14. A compound represented by any of the formulas (1-1) to (1-3). In formula (1-1), C Ａ This represents a ring expressed by any of the equations (2-1) to (2-3). Ｃ This represents the ring shown in equation (5). Note that C Ａ A ring represented by C Ｃ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with * in formula (5). In formula (1-2), C Ａ This represents a ring expressed by any of the equations (2-1) to (2-3). Ｂ１ This represents a ring expressed by any of the equations (3-1) to (3-5). Ｃ This represents the ring shown in equation (5). Note that C Ａ A ring represented by C Ｂ１ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with *1 in formulas (3-1) to (3-5). Ｂ１ A ring represented by C Ｃ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *2 in formulas (3-1) to (3-5) and the position of the carbon atom marked with * in formula (5). In formula (1-3), C Ａ This represents a ring expressed by any of the equations (2-1) to (2-3). Ｂ１ This represents a ring expressed by any of the equations (3-1) to (3-5). Ｂ２ This represents a ring expressed by any of the equations (4-1) to (4-5). Ｃ This represents the ring shown in equation (5). Note that C Ａ A ring represented by C Ｂ１ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *1 in formulas (2-1) to (2-3) and the position of the carbon atom marked with *1 in formulas (3-1) to (3-5). Ｂ１ A ring represented by C Ｂ２ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *2 in formulas (3-1) to (3-5) and the position of the carbon atom marked with *2 in formulas (4-1) to (4-5). Ｂ２ A ring represented by C Ｃ The ring represented by is formed by ring fusion between the position of the carbon atom marked with *3 in formulas (4-1) to (4-5) and the position of the carbon atom marked with * in formula (5). In formulas (2-1) to (2-3), formula (3-2), formula (3-3), formula (4-2), and formula (4-3), Z is independently -CR Ｚ１ = or represents a nitrogen atom. R Ｚ１ represents a hydrogen atom or a specific substituent. The specific substituent is -NR Ｎ ２ R represents substituents that do not contain either , or -CH=A. Ｎ Each independently represents a hydrogen atom or a substituent. A represents the group represented by formula (A-1). In formulas (2-2) to (2-3), formula (3-1), and formula (4-1), X independently represents a sulfur atom, an oxygen atom, and -NR Ｘ１ -, -SiR Ｘ２ ２ -, selenium atom, -GeR Ｘ３ ２ -, -CR Ｘ４ ２ -, or -C (=CR) Ｘ５ ２ ) represents R Ｘ１ ~R Ｘ５ Each independently represents a hydrogen atom or a substituent. In formulas (3-4), (3-5), (4-4), and (4-5), Y independently represents an oxygen atom, a sulfur atom, or -NR Ｙ１ Represents -. R Ｙ１ R represents a hydrogen atom or a substituent. In formulas (3-4), (3-5), (4-4), and (4-5), R independently represents a hydrogen atom or a substituent. In formula (5), R Ｘ Each of these independently represents a hydrogen atom or a substituent. Ｘ If all of them are substituents, R Ｘ These elements may join together to form a ring. Ｚ２ represents a hydrogen atom or substituent. A represents a group represented by formula (A-1). In formula (A-1), C １ Q represents a ring containing at least two carbon atoms, which may have substituents. Q represents an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ R represents a hydrogen atom or substituent. Ｑ２ and R Ｑ３ These are, independently, a cyano group and -SO ２ R Ｑ４ , -COOR Ｑ５ , -COR Ｑ６ , or -S(=O)R Ｑ７ Represents R Ｑ４ ~R Ｑ７ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position.

15. The compound according to claim 14, wherein A in formula (5) is a group represented by formula (C-1) or a group represented by formula (C-2). In formula (C-1), X ｃ１ and X ｃ２ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ ~R Ｑ３ These are R in formula (A-1) above, respectively. Ｑ１ ~R Ｑ３ This is synonymous with C. ３ X represents an aromatic ring which may have substituents. In formula (C-2), X ｃ３ ~X ｃ５ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ Represents R Ｑ１ ~R Ｑ３ These are R in formula (A-1) above, respectively. Ｑ１ ~R Ｑ３ This is synonymous with Z. ｃ１ and Z ｃ２ Each of these is independently -NR ｃ１ - or -CR ｃ２ ２ Represents -. R ｃ１ and R ｃ２ Each of these independently represents a hydrogen atom or a substituent. * indicates a bond position.

16. The compound according to claim 14, wherein the compound represented by formula (1-1) satisfies at least one of requirement A and requirement D, the compound represented by formula (1-2) satisfies at least one of requirement A, requirement B, and requirement D, and the compound represented by formula (1-3) satisfies at least one of requirement A, requirement B, requirement C, and requirement D. (Requirement A): C Ａ However, at least one of the four Zs is -CR Ｚ３ The ring represented by the above equation (2-1) =, where at least one of the two Zs is -CR Ｚ３ The ring represented by the above formula (2-2) =, or at least one of the two Zs is -CR Ｚ３ This represents the ring expressed by the above equation (2-3), where R = Ｚ３ This is a base represented by the following formula (Z). (Requirement B): C Ｂ１ However, at least one of the two Zs is -CR Ｚ３ A ring represented by the above formula (3-2) where =, or at least one of the two Zs is -CR Ｚ３ R represents the ring expressed by the above equation (3-3), where =. Ｚ３ This is the group represented by the above formula (Z). (Requirement C): C Ｂ２ However, at least one of the two Zs is -CR Ｚ３ A ring represented by the above formula (4-2) where =, or at least one of the two Zs is -CR Ｚ３ R represents the ring expressed by the above equation (4-3), where =. Ｚ３ is the group represented by formula (Z) above. (Requirement D): R in formula (5) above Ｚ２ However, this is the group represented by the above formula (Z). In formula (Z), Ar represents an aromatic ring group which may have the specified substituent. L represents a single bond, a divalent linking group represented by formula (L), or an ethynylene group. １ and R ２ Each of these independently represents a hydrogen atom or the specified substituent. * represents a bond position.

17. The compound according to claim 14, represented by formula (1-1).

18. In the above formulas (1-1) to (1-3), C Ａ The compound according to any one of claims 14 to 17, wherein the ring is represented by formula (2-1).

Images