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

Abstract

The present invention provides: a photoelectric conversion element having excellent manufacturability; and an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound, all of which relate to the photoelectric conversion element. This photoelectric conversion element includes, in the given order, a conductive film, a photoelectric conversion film, and a transparent conductive film. The photoelectric conversion film contains a compound represented by general formula (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 dye-sensitized solar cell containing a dye sensitizer of a specific structure.

[0003] Special table 2014-527086 publication

[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 of the characteristics required of photoelectric conversion elements is, for example, excellent manufacturability. In this specification, "excellent manufacturability" means that even when the rate at which compounds such as dyes are deposited is changed when fabricating the photoelectric conversion film in the photoelectric conversion element, the dark current characteristics of the resulting photoelectric conversion element change little regardless of the change in deposition rate. In particular, the photoelectric conversion element of the present invention is required to have excellent performance with respect to green-red light. The above-mentioned green-red light refers to light with a wavelength of 500 to 780 nm. Under these requirements, the inventors investigated a photoelectric conversion element containing a dye sensitizer disclosed in Patent Document 1 by fabricating it while changing the deposition rate of the dye sensitizer, and found that the change in the dark current characteristics of the resulting photoelectric conversion element was large depending on the deposition rate, indicating room for improvement.

[0005] Therefore, the present invention aims to provide a photoelectric conversion element with excellent manufacturability. 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 this order, wherein the photoelectric conversion film contains a compound represented by the general formula (1) described later. However, the compound represented by the general formula (1) does not contain any carboxyl group, salt of a carboxyl group, sulfonic acid group, salt of a sulfonic acid group, phosphate group, salt of a phosphate group, sulfinic acid group, or salt of a sulfinic acid group. [2] The photoelectric conversion element according to [1], wherein n1 and n2 are each independently 0 or 1. [3] The photoelectric conversion element according to [1] or [2], wherein ring A and ring B are each independently a ring structure represented by any one of the above formulas (D-1) to (D-3). [4] The photoelectric conversion element according to any one of [1] to [3], wherein ring C and ring D are each independently a ring structure represented by the above formula (D-6) or (D-9). [5] A １ However, the photoelectric conversion element is a group represented by the above formula (A-1) or a group represented by the above formula (A-2), as described in any one of [1] to [4]. [6] A １ However, the photoelectric conversion element according to any one of [1] to [5] is a group represented by the above formula (A-1) or a group represented by the above formula (A-2), and both m1 and m2 are 0. [7] W is >C=O, or >P(=O)R Ｐ１ A photoelectric conversion element as described in any one of [1] to [6]. [8] A １ However, it is a group represented by the above formula (A-1), or a hydrogen atom, and A ２ However, the photoelectric conversion element described in any one of [1] to [7] is a base represented by the above formula (A-1). [9] A １ However, it is a group represented by formula (A-3) described later, or a hydrogen atom, A ２The photoelectric conversion device according to any one of [1] to [8], which is a group represented by the above formula (A-3).

[10] The above photoelectric conversion film further contains an n-type organic semiconductor, and the above photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the above general formula (1) and the above n-type organic semiconductor are mixed. The photoelectric conversion device according to any one of [1] to [9].

[11] The photoelectric conversion device according to

[10] , wherein the above n-type organic semiconductor contains fullerenes selected from the group consisting of fullerene and its derivatives.

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

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

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

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

[14] The photoelectric conversion device according to any one of [1] to

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

[15] An imaging device having the photoelectric conversion device according to any one of [1] to

[14] .

[16] An optical sensor having the photoelectric conversion device according to any one of [1] to

[14] .

[17] A method for manufacturing an imaging device, which has a step of manufacturing the photoelectric conversion device according to any one of [1] to

[14] .

[18] A compound represented by the general formula (1) described later. However, the compound represented by the above general formula (1) does not have any of a carboxy group, a salt of a carboxy group, a sulfonic acid group, a salt of a sulfonic acid group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfinic acid group, and a salt of a sulfinic acid group.

[19] The compound according to

[18] , wherein n1 and n2 are each independently 0 or 1.

[20] The compound according to

[18] or

[19] , wherein the above ring A and the above ring B are each independently a ring structure represented by any one of the above formulas (D-1) to the above formula (D-3).

[21] The compound according to any one of

[18] to

[20] , wherein the ring C and the ring D are each independently a ring structure represented by the above formula (D-6) or the above formula (D-9).

[22] A １ The compound according to any one of

[18] to

[21] , which is a group represented by the above formula (A-1) or a group represented by the above formula (A-2).

[23] A １The compound according to any one of

[18] to

[22] , wherein the group is represented by the above formula (A-1) or the above formula (A-2), and both m1 and m2 are 0.

[24] W is >C=O, or >P(=O)R Ｐ１ The compound described in any one of

[18] to

[23] .

[25] A １ However, it is a group represented by the above formula (A-1), or a hydrogen atom, and A ２ However, the compound is one of the compounds listed in any one of

[18] to

[24] , which is represented by the above formula (A-1).

[26] A １ However, it is a group represented by formula (A-3) described later, or a hydrogen atom, A ２ However, the compound is one of the compounds listed in any one of

[18] to

[25] , which is a group represented by the above formula (A-3).

[0008] According to the present invention, a photoelectric conversion element with excellent manufacturability can be provided. 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, the asterisk (*) in formulas indicates a bonding position.

[0026] [Photoelectric Conversion Element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in that order, wherein the photoelectric conversion film contains a compound represented by the general formula (1) described later (hereinafter also referred to as the "specific compound").

[0027] The reason why the 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 still within the scope of the present invention. The specific compound of the present invention has a specific divalent group represented by W, which deepens the HOMO level, resulting in a smaller dark current compared to the case where the specific divalent group is not present. Furthermore, the specific compound does not contain predetermined acid groups, etc., and has a specific donor structure and acceptor structure, thus suppressing aggregation in the film state, and enabling stable film formation even when the deposition rate is changed. As a result of the above, the photoelectric conversion element of the present invention is considered to have excellent manufacturability. Hereinafter, superior manufacturability will also be referred to as "the effect of the present invention is superior."

[0028] Figure 1 shows a schematic cross-sectional view of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 that functions as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 that functions as an upper electrode are stacked in this order. Figure 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in Figure 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked on the lower electrode 11 in this order. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figures 1 and 2 may be appropriately changed depending on the application and characteristics.

[0029] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Furthermore, when using the photoelectric conversion element 10a (or 10b), a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and between this pair of electrodes, 1 × 10⁻¹⁰ －５ ~1 x 10 ７It is preferable to apply a voltage of V / cm. In terms of performance and power consumption, the applied voltage should be 1 × 10⁻⁶. －４ ~1 x 10 ７ V / cm is more preferable, 1 × 10 －３ ~5 x 10 ６ A voltage of V / cm is even more preferable. Regarding the voltage application method, 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, as shown in Figures 1 and 2. The same method can be used to apply the voltage when the photoelectric conversion element 10a (or 10b) is used as a light sensor or when it is incorporated into an image sensor. As will be described in detail later, the photoelectric conversion element 10a (or 10b) is suitably applicable to image sensor applications. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

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

[0031] <Specific Compounds> The photoelectric conversion film contains a compound represented by general formula (1).

[0032]

[0033] In general formula (1), W is >C=O, >C=S, >P(=O)R Ｐ１ ,>S(=O) ２ R represents a divalent group selected from , and >S=O. Ｐ１ represents a hydrogen atom or substituent. For superior effects of the present invention, W can be >C=O, >C=S, or >P(=O)R Ｐ１ Preferably, C=O, or >P(=O)R Ｐ１ This is more preferable. Ｐ１ A substituent is preferred for R Ｐ１ Examples of substituents represented by include those exemplified by substituent W described above, and preferably are an aliphatic hydrocarbon group which may have substituents, an aromatic ring group which may have substituents, or an aliphatic heterocyclic group which may have substituents.

[0034] 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.

[0035] The above 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 either 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 10, and even more preferably 5 to 6. 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 above aromatic heterocyclic group are as described above, with a thiophene ring group, a furan ring group, or a pyridine ring group being preferred.

[0036] The definition of an aliphatic heterocyclic group is as described above. In an aliphatic heterocyclic group that may have substituents, the number of ring members of the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8. The number of carbon atoms in the aliphatic heterocyclic group is preferably 1 to 20. Examples of heteroatoms that the aliphatic heterocyclic group may have include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen atoms being preferred.

[0037] In the above general formula (1), n1 and n2 each independently represent integers from 0 to 3. In terms of superior effects of the present invention, n1 and n2 are each preferably integers from 0 to 2, more preferably 0 or 1, and even more preferably both be 0. m1 and m2 each independently represent integers from 0 to 2. For m1 and m2, each is preferably 0 or 1, and even more preferably both be 0. Among these, A, which will be described later, １ However, if the group is represented by formula (A-1) or formula (A-2), it is preferable that m1 and m2 are each independently 0 or 1. １ When is a hydrogen atom, it is preferable that at least one of m1 and m2 is 1, and more preferably that m1 is 1.

[0038] In the above general formula (1), A １ A represents the group represented by formula (A-1), which will be described in detail later, the group represented by formula (A-2), which will be described in detail later, or a hydrogen atom. ２ This represents a group represented by the above formula (A-1) or a group represented by the above formula (A-2).

[0039] In the above general formula (1), ring A and ring B each independently represent a ring structure represented by any of the following formulas (D-1) to (D-5). Also, ring C and ring D each independently represent a ring structure represented by any of the following formulas (D-6) to (D-10). However, when both n1 and n2 are 0, at least one of ring C and ring D is a ring structure represented by any of the above formulas (D-6) to (D-8). Ring A and ring B each independently preferably represent a ring structure represented by any of the following formulas (D-1) to (D-3), and more preferably a ring structure represented by formula (D-1) or formula (D-2). Ring C and ring D preferably represent a ring structure represented by any of the following formulas (D-6), (D-9), and (D-10), and more preferably a ring structure represented by formula (D-6) or formula (D-9).

[0040]

[0041] In formulas (D-1) to (D-10), * and *b represent bond positions, and when ring C represents a ring structure represented by any of formulas (D-6) to (D-10), *b in formulas (D-6) to (D-10) is A １ The bond position on the side is represented, and when ring D represents a ring structure represented by any of the formulas (D-6) to (D-10), *b in formulas (D-6) to (D-10) is A ２ This represents the bond position on the side. For example, in general formula (1), n1=n2=1, m1=m2=0, A １ A is a hydrogen atom, A ２ An example of a compound represented by general formula (1) is shown below, where is a group represented by formula (A-1), which will be described in detail later, rings A and B are groups represented by formula (D-1), and rings C and D are groups represented by formula (D-6).

[0042]

[0043] In equations (D-1) to (D-10), Y is independently -CR Ｙ１ = or represents a nitrogen atom. R Ｙ１ represents a hydrogen atom or substituent. In terms of the superior effects of the present invention, Y is always -CR Ｙ１ It is preferable that it is equal to R. Ｙ１ R is preferably a hydrogen atom, an optionally substituted aromatic ring group, or an optionally substituted aliphatic hydrocarbon group. Ｙ１ Examples of substituents represented by include those exemplified by substituent W above, and preferably are optionally substituted aromatic ring groups, optionally substituted aliphatic hydrocarbon groups, or halogen atoms. Specific examples of optionally substituted aliphatic hydrocarbon groups and optionally substituted aromatic ring groups are shown in R Ｐ１ The substituents represented by are as described in detail. As halogen atoms, for example, fluorine atoms or chlorine atoms are preferred.

[0044] In formula (D-1), X １ These are sulfur atoms, oxygen atoms, >C=O, >P(=O)R Ｄ１ , >C=S, >S=O, >S(=O) ２ ,>CR Ｄ２ R Ｄ３ ,>NRＤ４ , selenium atom, tellurium atom, >SiR Ｄ５ R Ｄ６ ,>GeR Ｄ７ R Ｄ８ , or >P(=S)R Ｄ９ Represents R Ｄ１ ~R Ｄ９ Each of these independently represents a hydrogen atom or a substituent. １ Examples include sulfur atoms, oxygen atoms, >C=O, >P(=O)R Ｄ１ , >C=S, >S=O, >S(=O) ２ ,>CR Ｄ２ R Ｄ３ , or >NR Ｄ４ Preferably, sulfur atom, oxygen atom, >C=O, >P(=O)R Ｄ１ More preferably, >C=S, and even more preferably, a sulfur atom, an oxygen atom, or >C=O.

[0045] R Ｄ１ ~R Ｄ９ A substituent is preferred, R Ｄ１ ~R Ｄ９ Examples of substituents represented by the above-mentioned substituent W include the substituents exemplified above, and preferably are substituted aliphatic hydrocarbon groups, substituted aromatic ring groups, or substituted aliphatic heterocyclic groups. Specific examples of substituted aliphatic hydrocarbon groups, substituted aromatic ring groups, and substituted aliphatic heterocyclic groups are shown in R Ｐ１ The substituents represented by have been described in detail.

[0046] In formula (D-4), V １ is an oxygen atom, a sulfur atom or >NR Ｖ１ Represents R Ｖ１ V represents a hydrogen atom or substituent. １ As such, an oxygen atom is preferred. Ｖ１ A substituent is preferred for R Ｖ１Examples of the substituent represented by [the substituent represented by] are, for example, the substituents exemplified by the above-described substituent W, and an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent are preferable. Specific examples of the aliphatic hydrocarbon group which may have a substituent, the aromatic ring group which may have a substituent, and the aliphatic heterocyclic group which may have a substituent are as described in detail for the substituent represented by R Ｐ１ as described in detail for the substituent represented by [the substituent represented by].

[0047] In formula (D-4), V ２ and V ３ each independently represents a hydrogen atom or a substituent. As V ２ and V ３ , a substituent is preferable. Examples of the substituent represented by V ２ or V ３ are, for example, the substituents exemplified by the above-described substituent W, and an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent are preferable. Specific examples of the aliphatic hydrocarbon group which may have a substituent, the aromatic ring group which may have a substituent, and the aliphatic heterocyclic group which may have a substituent are as described in detail for the substituent represented by R Ｐ１ as described in detail for the substituent represented by [the substituent represented by].

[0048] In formula (D-5), V ４ represents an oxygen atom, a sulfur atom or >NR Ｖ１ . R Ｖ１ represents a hydrogen atom or a substituent. As V ４ , an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable. As R Ｖ１ , a substituent is preferable. Examples of the substituent represented by R Ｖ１ are, for example, the substituents exemplified by the above-described substituent W, and an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent are preferable. In formula (D-5), V ５ represents an oxygen atom or a sulfur atom. As V ５ , an oxygen atom is preferable.

[0049] In formulas (D-6) to (D-8), X ２Each independently represents a sulfur atom, an oxygen atom, >NR Ｄ１０ , a selenium atom or a tellurium atom. R Ｄ１０ represents a hydrogen atom or a substituent. X ２ is preferably a sulfur atom or an oxygen atom, more preferably a sulfur atom. R Ｄ１０ is preferably a substituent, and R Ｄ１０ Examples of the substituent represented by include, for example, the substituents exemplified by the above-mentioned substituent W, and an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent are preferred. Specific examples of the aliphatic hydrocarbon group which may have a substituent, the aromatic ring group which may have a substituent, and the aliphatic heterocyclic group which may have a substituent are as detailed for the substituent represented by R Ｐ１ .

[0050] In the above general formula (1), ring E and ring F each independently represent a monocyclic aromatic ring group or a conjugated ring group of a 2- to 4-ring condensed ring. The monocyclic aromatic ring group and the conjugated ring group of the 2- to 4-ring condensed ring may have a substituent. The number of substituents that the above monocyclic aromatic ring group and the above condensed ring conjugated ring group may have is not particularly limited, but 1 to 3 is preferred, and 1 is more preferred. Examples of the substituents that the above monocyclic aromatic ring group and the above condensed ring conjugated ring group may have include the groups exemplified by the above substituent W, and among them, groups selected from the following substituent group S are preferred. Substituent group S: an aromatic ring group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an acyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, and -Si(R Ｓｉ１ ). ３ .

[0051] In the substituent group S, specific examples of the aliphatic hydrocarbon group which may have a substituent, the aromatic ring group which may have a substituent, and the aliphatic heterocyclic group which may have a substituent are as detailed for the substituent represented by R Ｐ１ .

[0052] In the substituent group S, the number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

[0053] Among the substituent group S, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred.

[0054] -Si(R) in the substituent group S Ｓｉ１ ) ３ In R Ｓｉ１ This represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. Examples of substituents that may be present on the aliphatic hydrocarbon group, aromatic ring group, and aliphatic heterocyclic group include the groups exemplified by substituent W. Ｓｉ１ The optionally substituted aliphatic hydrocarbon group, optionally substituted aromatic ring group, and optionally substituted aliphatic heterocyclic group represented by are synonymous with the optionally substituted aliphatic hydrocarbon group, optionally substituted aromatic ring group, and optionally substituted aliphatic heterocyclic group in substituent group S. Ｓｉ１ Among these, aliphatic hydrocarbon groups are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred.

[0055] The monocyclic aromatic ring group represented by ring E or ring F may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The number of members in the aromatic ring group is preferably 5 to 10, more preferably 5 to 8, and even more preferably 5 to 6. The definition and specific examples of the aromatic hydrocarbon group are as described above, and an aromatic ring group obtained by removing a hydrogen atom from a benzene ring is preferred. Examples of heteroatoms in the aromatic heterocyclic group include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen atoms being preferred. The definition and specific examples of the aromatic heterocyclic group are as described above, and a thiophene ring group, a furan ring group, or a pyridine ring group is preferred, with a thiophene ring group or a furan ring group being more preferred.

[0056] The conjugated ring group of the 2-4 ring fusion described above, represented by ring E or ring F, does not have to be aromatic, but it is preferable that it be an aromatic ring group of the 2-4 ring fusion described above. The number of rings contained in the conjugated ring group is preferably 2 or 3, more preferably 2. The number of ring members of the conjugated ring group is preferably 8 to 20, more preferably 8 to 15, and even more preferably 8 to 10. The conjugated ring group may have heteroatoms as ring member atoms, and examples of heteroatoms include sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred.

[0057] As described above, in the general formula (1) above, A １ A represents the group represented by formula (A-1), the group represented by formula (A-2), or a hydrogen atom. ２ This represents a group represented by formula (A-1) or a group represented by formula (A-2). In terms of the superior effects of the present invention, A １ It is preferable that the group is represented by the above formula (A-1) or the above formula (A-2), and more preferably the group is represented by the above formula (A-1). ２ It is preferable that the group is represented by the above formula (A-1). Also, A １ However, it is also preferable that the group is represented by the above formula (A-1) or the above formula (A-2), and that both m1 and m2 are 0. １ However, it is a group represented by the above formula (A-1), or a hydrogen atom, and A ２ However, the group represented by formula (A-1) above is also preferable. The group represented by formula (A-1) and the group represented by formula (A-2) will be described in detail below.

[0058]

[0059] In equations (A-1) to (A-2), *b represents the bonding position. In equation (A-1), R １ R represents a hydrogen atom or substituent. In terms of the superior effects of the present invention, １ Hydrogen atoms are preferred. Cy １ This represents a ring containing two or more carbon atoms, which may have substituents. １The two carbon atoms included are the two carbon atoms explicitly shown in formula (A-1). The number of carbon atoms in the ring is preferably 2 to 30, more preferably 2 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the two carbon atoms explicitly shown in the formula. The ring may be either an aromatic ring or an aliphatic ring. The 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 ring may have heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with sulfur, nitrogen, or oxygen being preferred. The number of heteroatoms that the ring may have is preferably 0 to 10, and more preferably 0 to 5. The above Cy １ Among the carbon atoms constituting the ring represented by formula (A-1), the carbon atoms at the bond positions marked with *b and Q １ Carbon atoms other than those bonded to may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S).

[0060] Examples of substituents that the above ring may have include the substituent W described above, which is preferably a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic ring group, or a silyl group, with a halogen atom or alkyl group being more preferred. The alkyl group may be linear, branched, or cyclic, with a linear configuration being preferred. The alkyl group has 1 to 10 carbon atoms, and 1 to 3 carbon atoms being more preferred. Preferred substituents that the alkyl group may have are a halogen atom, an aromatic ring group, or a silyl group. Preferred substituents that the aromatic ring group may have are a halogen atom, an alkyl group, or a silyl group.

[0061] The ring represented by formula (A-1) is preferably a ring used as an acidic nucleus (for example, an acidic nucleus made of merocyanine dye), and examples of such 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 nuclei: For example, barbituric acid, 2-thiobarbituric acid, and their 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) 2,4-imidazolidinedione (hydantoin) core: e.g., 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione. (g) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) core: e.g., 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione. (h) imidazolin-5-one core: e.g., 2-propylmercapto-2-imidazolin-5-one. (i) 3,5-pyrazolidinedione core: e.g., 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione.(j) Indanone nuclei: e.g., 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone, etc. (k) Benzofuran-3-(2H)-one nuclei: e.g., benzofuran-3-(2H)-one, etc. (l) 2,2-dihydrophenalen-1,3-dione nuclei, etc.

[0062] In the above formula (A-1), Q １ This consists of an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｑ１ represents a hydrogen atom or a substituent. Examples of substituents include the substituent W described above, and preferred substituents are an aliphatic hydrocarbon group which may have substituents, an aromatic ring group which may have substituents, or an aliphatic heterocyclic group which may have substituents. Examples of substituents which each group may have include those exemplified by substituent W above. The definition of an aliphatic hydrocarbon group is as described above, and an aliphatic hydrocarbon group having 1 to 4 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 preferred heteroatoms of the aliphatic heterocyclic group are a sulfur atom, an oxygen atom, or a nitrogen atom. Ｑ２ and R Ｑ３ These are, independently, a cyano group and -C(=O)OR Ｑ４ , -C(=O)R Ｑ５ , -S(=O)R Ｑ６ , or -S (=O) ２ 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. The definitions and preferred embodiments of each group are shown in R Ｑ１ These are the same groups as the substituents exemplified by the formulas.

[0063] In formula (A-2), R ２R represents a hydrogen atom or substituent. In terms of the superior effects of the present invention, ２ A hydrogen atom is preferred. ｂ１ and R ｂ２ These are, independently, a cyano group and -C(=O)OR ｂ３ , -C(=O)R ｂ４ , -S(=O)R ｂ５ , or -S (=O) ２ R ｂ６ This represents the superior effect of the present invention, R ｂ１ and R ｂ２ Preferably, at least one of them is a cyano group, R ｂ１ and R ｂ２ It is more preferable that it is a cyano group. ｂ３ ~R ｂ６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ｂ３ ~R ｂ６ The definitions and preferred embodiments of each group represented by R Ｑ４ ~R Ｑ７ It is the same as the base represented by .

[0064] As the group represented by the above formula (A-1), the group represented by formula (A-3) is preferred. Furthermore, in terms of the superior effects of the present invention, in the above general formula (1), A １ However, it is a group represented by formula (A-3), or a hydrogen atom, and A ２ However, it is preferable that the group is represented by the above formula (A-3).

[0065]

[0066] In formula (A-3), R １ And *b is R in formula (A-1) above. １ This is synonymous with *b. ２ This represents a ring containing three or more carbon atoms, which may have substituents. ２The three carbon atoms included are the three carbon atoms explicitly shown in formula (A-3). 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 an aliphatic 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. The above Cy ２ Among the carbon atoms constituting the ring represented by the formula (A-3), the carbon atoms at the bond positions marked with *b, and Q ２ Or Q ３ Carbon atoms other than those bonded to may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S).

[0067] In the above formula (A-3), 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 represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ｑ２ and R ｑ３ These are, independently, a cyano group and -C(=O)OR ｑ４ , -C(=O)R ｑ５ , -S(=O)R ｑ６ , or -S (=O) ２ R ｑ７ Represents R ｑ４ ~R ｑ７Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. Q ２ and Q ３ The definitions and preferred embodiments of each group represented by the above formula (A-1) are as follows: １ Each group represented is the same as R. ｑ１ ~R ｑ７ The definitions and preferred embodiments of each group represented by the above formula (A-1) are as follows: Ｑ１ ~R Ｑ７ These are the same as each of the groups represented by .

[0068] The group represented by formula (A-1) is more preferably the group represented by formula (A-4) or formula (A-5) in terms of superior effects of the present invention. Furthermore, the group represented by formula (A-2) is more preferably the group represented by formula (A-6) in terms of superior effects of the present invention.

[0069]

[0070] In equations (A-4) and (A-5), R １ And *b is R in formula (A-1) above. １ This is synonymous with *b. In formula (A-6), R ２ And *b is R in the above formula (A-2) ２ This is synonymous with *b.

[0071] In formula (A-4), Q ４１ ~Q ４３ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ In terms of the superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. In terms of the superior effects of the present invention, Q ４１ and Q ４３ It is preferable that Q is an oxygen atom. ４１ ~Q ４３ It is more preferable that it is an oxygen atom. Ｑ１ ~R Ｑ３ These are, respectively, R in the above formula (A-1). Ｑ１ ~R Ｑ３ It is synonymous with [the above].

[0072] In the above formula (A-4), Z ａ５１ and Z ａ５２ Each of these is independently -NR ａ５７ - or -C (R ａ５８ ) (Caution ａ５９ )- represents the fact that the effects of the present invention are superior, -NR ａ５７ - is preferable. R ａ５７ ~R ａ５９ 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.

[0073] In formula (A-5), Q ５１ and Q ５２ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｑ１ , or =CR Ｑ２ R Ｑ３ This represents the superior effect of the present invention, and uses an oxygen atom, a sulfur atom, or =CR Ｑ２ R Ｑ３ This is preferable, and an oxygen atom is more preferable. Ｑ１ ~R Ｑ３ These are, respectively, R in the above formula (A-1). Ｑ１ ~R Ｑ３ It is synonymous with [the above].

[0074] In formula (A-5), Cy ３represents an aromatic ring containing two or more carbon atoms and which may have substituents. The aromatic ring may be monocyclic or polycyclic. The number of ring 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 ring member atoms of the aromatic ring is the number including the two carbon atoms explicitly shown in the formula. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. Specific examples of the aromatic ring are as described above, and are 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 include the groups exemplified by substituent W, and alkyl groups or halogen atoms are preferred. The number of substituents that the above aromatic ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.

[0075] The specified compound does not contain any carboxyl group, salt of a carboxyl group, sulfonic acid group, salt of a sulfonic acid group, phosphate group, salt of a phosphate group, sulfinic acid group, or salt of a sulfinic acid group.

[0076] The following are specific examples of particular compounds, but the present invention is not limited to these.

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] Specific examples of the group represented by A are shown below.

[0085]

[0086]

[0087]

[0088]

[0089] The molecular weight of the specific compound is preferably 350 to 1200, more preferably 450 to 1000, and even more preferably 450 to 950. It is presumed that when the molecular weight is as described above, the sublimation temperature of the specific compound will be lower, resulting in superior manufacturing suitability.

[0090] The specific compound is preferably one with a single-film ionization potential of -5.0 to -6.0 eV.

[0091] The maximum absorption wavelength of the specific compound is preferably 400 to 900 nm, more preferably 450 to 800 nm, and even more preferably 450 to 700 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.

[0092] The specific compound is particularly useful as a material for photoelectric conversion films used in image sensors, optical sensors, or photocells. The photoelectric conversion film only needs to contain the specific compound; the function and mechanism of action of the specific compound in the photoelectric conversion film are not particularly limited. In other words, the specific compound may be, for example, a dye or an n-type organic semiconductor in the photoelectric conversion film. 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 material.

[0093] 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.

[0094] 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.

[0095] <n-type organic semiconductor> In addition to the specified compounds mentioned above, the photoelectric conversion film may also contain an n-type organic semiconductor. An n-type organic semiconductor is an acceptor organic semiconductor material (compound), which is an organic compound that readily accepts electrons. In other words, an n-type organic semiconductor is the organic compound with the greater electron affinity when two organic compounds are brought into contact. Therefore, any organic compound with electron-accepting properties can be used as an acceptor organic semiconductor. Examples of n-type organic semiconductors other than specific compounds 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 thiazoline). Examples include: zoles, 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 compounds described in paragraphs

[0056] to

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

[0096] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and their derivatives are preferred. For example, fullerene C ６０ , Fullerene C ７０ , Fullerene C ７６, Fullerene C ７８ , Fullerene C ８０ , Fullerene C ８２ , Fullerene C ８４ , Fullerene C ９０ , Fullerene C ９６ , Fullerene C ２４０ , Fullerene C ５４０ 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.

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

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

[0099] The photoelectric conversion film preferably has a bulk heterostructure formed in a state in which a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in the photoelectric conversion film in which 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.

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

[0101] 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%.

[0102] 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.

[0103] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness 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%.

[0104] Furthermore, it is preferable that the photoelectric conversion film is substantially composed of a specific compound, an n-type organic semiconductor, and a p-type organic semiconductor as desired. "Substantially" means that the total content of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100%, and more preferably 99 to 100%. In another embodiment, the photoelectric conversion film may also contain a specific compound, a p-type organic semiconductor, and a dye as desired, and is more preferably substantially composed of a specific compound, a p-type organic semiconductor, and a dye as desired. "Substantially" means that the total content of the specific compound, the p-type organic semiconductor, and the dye relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100%, and more preferably 99 to 100%. The p-type organic semiconductor and the dye will be described in detail later.

[0105] <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.

[0106] 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.

[0107]

[0108]

[0109]

[0110]

[0111] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or greater.

[0112] 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%.

[0113] 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.

[0114] <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.

[0115] 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.

[0116] 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%.

[0117] <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.

[0118] 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.

[0119] [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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] [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.

[0124] <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.

[0125] 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.

[0126] <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.

[0127] 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.

[0128] 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.

[0129] [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.

[0130] [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.

[0131] [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.

[0132] [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.

[0133] [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.

[0134] [Compounds] This invention also includes inventions of specific compounds.

[0135] 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.

[0136] [Compounds used in photoelectric conversion films] The following lists the materials used in the photoelectric conversion films.

[0137] [Synthesis of Compound 1-1] Compound 1-1 was synthesized according to the following scheme.

[0138]

[0139] <Synthesis of Compound (1-1-2)> 20.0 g (41.5 mmol) of compound (1-1-1) and 200 mL of tetrahydrofuran (THF) were placed in a glass reaction vessel, and the internal temperature was cooled to below -60°C in a dry ice-acetone bath under a nitrogen atmosphere. 38 mL (93.4 mmol) of 2.5 M n-BuLi (n-butyllithium) was added dropwise to the resulting mixture at an internal temperature of below -60°C, and the mixture was stirred for 1 hour. Then, 8.03 mL (104 mmol) of dimethylformamide (DMF) was added dropwise at an internal temperature of below -60°C, and the mixture was heated to room temperature. 6 M hydrochloric acid was added to the resulting reaction solution, and the precipitated solid was sequentially washed with water and methanol to obtain 13.7 g (36.0 mmol, yield 86.8%) of compound (1-1-2).

[0140] <Synthesis of Compound (1-1-3)> 13.7 g (36.0 mmol) of compound (1-1-2), 340 mL of toluene, 18.8 g (180 mmol) of 2,2-dimethyl-1,3-propanediol, and 0.617 g (3.24 mmol) of p-toluenesulfonic acid were placed in a glass reaction vessel and reacted at 120°C under a nitrogen atmosphere for 2 hours. The resulting reaction mixture was allowed to cool to room temperature, 5 mL of triethylamine was added, ethyl acetate and water were added, and the mixture was separated. The organic layer was washed with water until the 2,2-dimethyl-1,3-propanediol was removed, and the organic layer was dried over sodium sulfate. The solvent was then removed under reduced pressure. The resulting concentrate was purified by aminosilica gel column chromatography, and the filtrate obtained by suspending it in hexane-ethyl acetate was dried to obtain 7.67 g (13.9 mmol, yield 38.5%) of compound (1-1-3).

[0141] <Synthesis of Compound (1-1-4)> 5.20 g (9.42 mmol) of compound (1-1-3) and 47 mL of THF were placed in a glass reaction vessel, and the internal temperature was cooled to below -60°C using a dry ice-acetone bath. To the resulting solution, 7.16 mL (19.8 mmol) of 2.76 M n-butyllithium was added dropwise at an internal temperature of below -60°C, and the mixture was stirred for 1 hour. Subsequently, 1.91 mL (20.7 mmol) of dimethylcarbamoyl chloride was added dropwise at an internal temperature of below -60°C, and the mixture was stirred for 15 minutes. Then, the dry ice-acetone bath was changed to an ice water bath, and the mixture was stirred for a further 1 hour. Saturated ammonium chloride solution was added to the resulting reaction mixture, and it was extracted with dichloromethane. The organic layer was washed with saturated brine, dried over sodium sulfate, and the solvent was removed under reduced pressure. The concentrate was purified by aminosilica gel column chromatography and recrystallized with dichloromethane-methanol to obtain 2.36 g (5.61 mmol, yield 59.6%) of compound (1-1-4).

[0142] <Synthesis of Compound (1-1-5)> 590 mg (1.43 mmol) of compound (1-1-4) and 18 mL of THF were placed in a glass reaction vessel, and 5 mL of 30% hydrochloric acid was added. The mixture was stirred at 90°C for 5 hours under a nitrogen atmosphere. After cooling the resulting reaction solution with ice, the precipitated solid was filtered and dried to obtain 317 mg (1.28 mmol, yield 91.0%) of compound (1-1-5).

[0143] <Synthesis of Compound (1-1)> 200 mg (0.806 mmol) of compound (1-1-5), 327 mg (2.09 mmol) of 1,3-dimethylbarbituric acid, 20 mL of toluene, and 27.4 mg (0.322 mmol) of piperidine were placed in a glass reaction vessel and reacted at 110°C for 2 hours under a nitrogen atmosphere. The resulting reaction solution was allowed to cool to room temperature, and the precipitated solid was filtered and dried under vacuum. The obtained solid was purified by sublimation to obtain 275 mg (0.524 mmol, yield 65.0%) of compound (1-1). Since compound (1-1) is sparingly soluble, its structure was confirmed by LDI-MS (laser desorption / ionization mass spectrometry). LDI-MS: 524.1 (M ＋ )

[0144] The compounds used in each example and comparative example for photoelectric conversion films other than compound (1-1) are synthesized in accordance with the synthesis method of compound (1-1).

[0145] [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-4) are comparative compounds, while the other compounds are specific compounds.

[0146]

[0147]

[0148]

[0149]

[0150] [n-type organic semiconductor] ・C ６０ : Fullerene (C ６０ )

[0151] [p-type organic semiconductor]

[0152]

[0153] [Evaluation] A photoelectric conversion element will be fabricated using the above materials, and the following tests X and Y will be performed.

[0154] [Test X] A photoelectric conversion element will be fabricated as described below, and its quantum efficiency, response speed, dependence of quantum efficiency on electric field strength, and manufacturability will be evaluated when it receives green-red light (wavelength 570 nm).

[0155] <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. ６０A 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 O ３ 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.

[0156]

[0157] <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.

[0158] <Quantum Efficiency> For each photoelectric conversion element, the quantum efficiency when receiving green-red 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 570 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 in 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.

[0159] A: 0.90 or higher B: 0.80 or higher, less than 0.90 C: 0.70 or higher, less than 0.80 D: 0.60 or higher, less than 0.70 E: Less than 0.60

[0160] <Response Speed> The response speed of each photoelectric conversion element when receiving green-red light is evaluated using the following method. 2.0 × 10⁻¹⁶ ５ A 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 570 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 (= (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element in Example 1-1)) is determined, with the rise time of the above photoelectric conversion element of Example 1-1 set to 1, and the response speed is evaluated according to the evaluation criteria below.

[0161] A: Less than 1.1 B: 1.1 or more, less than 1.5 C: 1.5 or more, less than 2.0 D: 2.0 or more

[0162] <Dependence of quantum efficiency on electric field strength> For each photoelectric conversion element, the dependence of the quantum efficiency on electric field strength when receiving green-red light is evaluated using the following method. In the evaluation of <quantum efficiency> above, the voltage applied to each photoelectric conversion element is 7.5 × 10 ４ Except for changing to V / cm, the procedure was the same: 7.5 × 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. 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 570 nm for the photoelectric conversion element of Example 1-1 is 7.5 × 10⁻¹⁰. ４ Photoelectric conversion efficiency at V / cm and the electric field strength of the photoelectric conversion element in Example 1-1 at a wavelength of 570 nm (2.0 × 10⁻¹⁰) ５This 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 7.5 × 10⁻⁶) ４ (Photoelectric conversion efficiency at V / cm) / (Applied voltage to each photoelectric conversion element 2.0 × 10⁻¹⁰) ５ Photoelectric conversion efficiency in V / cm)

[0163] A: The dependence of quantum efficiency on electric field strength is 0.9 or higher. B: The dependence of quantum efficiency on electric field strength is 0.8 or higher and less than 0.9. C: The dependence of quantum efficiency on electric field strength is 0.7 or higher and less than 0.8. D: The dependence of quantum efficiency on electric field strength is less than 0.7.

[0164] <Manufacturability> The manufacturability of each photoelectric conversion element is evaluated using the following method. In the above <Fabrication of Photoelectric Conversion Elements>, except that the film deposition rate of the photoelectric conversion film 12 is set to 2.0 Å / sec, a photoelectric conversion element (B) is fabricated using the same procedure as in the above <Dark Current>, and the dark current of the photoelectric conversion element (B) is measured using the same method as in the above <Dark Current>. The photoelectric conversion element obtained in the above [Fabrication of Photoelectric Conversion Elements], in which the film deposition rate of the photoelectric conversion film 12 is 1.0 Å / sec, is designated as photoelectric conversion element (A), and the relative ratio of dark currents B / A (= dark current of photoelectric conversion element (B) / dark current of photoelectric conversion element (A)) is calculated. From the obtained values, the manufacturability is evaluated according to the evaluation criteria below. The closer the value of the relative ratio B / A is to 1, the less the performance of the photoelectric conversion element deteriorates even during high-speed film deposition, indicating superior manufacturability. A manufacturability evaluation of C or higher is preferable.

[0165] A: Relative ratio B / A is less than 1.1 B: Relative ratio B / A is 1.1 or greater, but less than 1.3 C: Relative ratio B / A is 1.3 or greater, but less than 1.5 D: Relative ratio B / A is 1.5 or greater

[0166] [Results (Test X)]

[0167] The evaluation results are shown in Table 1 below. In the table, the "n1, n2 = 0 or 1" column is "A" if n1 and n2 in general formula (1) are each independently 0 or 1, and "B" otherwise. In the table, the "Ring A, B" column is "A" if ring A and ring B in general formula (1) are each independently ring structures represented by any of the above formulas (D-1) to (D-3), or if both n1 and n2 are 0, and "B" otherwise. In the table, the "Ring C, D" column is "A" if ring C and ring D in general formula (1) are each independently ring structures represented by formula (D-6) or formula (D-9), and "B" otherwise. １ The column "= (A-1), (A-2)" is where A in general formula (1) １ However, if the group is represented by formula (A-1) or formula (A-2), it is designated as "A", and in all other cases, it is designated as "B". In the table, "m1, m2 = 0, A １ The column "= (A-1), (A-2)" is where A in general formula (1) １ However, if the group is represented by formula (A-1) or formula (A-2) and both m1 and m2 are 0, it is classified as "A", and in all other cases, it is classified as "B". In the table, "C=O,>P(=O)R Ｐ１ The column indicates that in general formula (1), W is >C=O or >P(=O)R. Ｐ１ If this is the case, it is designated as "A", and otherwise it is designated as "B". In the table, the "(A-1)" column is where A is in general formula (1). １ However, it is a group represented by the above formula (A-1), or a hydrogen atom, and A ２ However, if the base is represented by the above formula (A-1), it is designated as "A", and otherwise it is designated as "B". In the table, the "(A-3)" column is where A is represented in general formula (1). １ However, it is a group represented by formula (A-3), or a hydrogen atom, and A ２ However, if the base is represented by formula (A-3), it is designated as "A," and in all other cases, it is designated as "B."

[0168]

[0169] The results shown in Table 1 demonstrate that the photoelectric conversion element of the present invention exhibits excellent manufacturability. Furthermore, the photoelectric conversion element of the present invention exhibits excellent quantum efficiency, response speed, and electric field strength dependence of quantum efficiency when receiving green-red light.

[0170] From comparisons of Examples 1-33 to 1-35, it is shown that when n1 and n2 in general formula (1) are independently 0 or 1, manufacturability is superior. From comparisons of Examples 1-28, 1-29, 1-31, 1-33, 1-34 and 1-36, it is shown that when at least one of n1 and n2 in general formula (1) is an integer from 1 to 3, when ring A and ring B are independently ring structures represented by any of the above formulas (D-1) to (D-3), manufacturability is superior. From comparisons of Examples 1-28, 1-29, 1-31, 1-33, 1-34 and 1-37, it is shown that when ring C and ring D in general formula (1) are independently ring structures represented by formula (D-6) or formula (D-9), quantum efficiency, response speed, and the electric field strength dependence of quantum efficiency are superior. From comparisons between Examples 1-28, 1-29, 1-31, 1-33, and 1-34 and 1-13 to 1-27, etc., in general formula (1), A １ However, it is shown that the quantum efficiency is better when the group is represented by formula (A-1) or formula (A-2). Comparisons of Examples 1-13 to 1-27 show that in general formula (1), A １ However, when the group is represented by formula (A-1) or formula (A-2), and both m1 and m2 are 0, it is shown that the manufacturability is superior. From a comparison of Examples 1-4 and 1-12, etc., in general formula (1), W is >C=O, >P(=O)R Ｐ１ If C=S, the quantum efficiency is better, and from comparisons between Examples 1-4 and 1-12 and 1-13 to 1-18, W is >C=O, or >P(=O)R Ｐ１ In this case, it was confirmed that the manufacturability is superior. From a comparison between Examples 1-7 and other examples, etc., in general formula (1), A １ However, it is a group represented by the above formula (A-1), or a hydrogen atom, and A ２However, it is shown that the quantum efficiency is better when the group is represented by the above formula (A-1). From a comparison of Examples 1-28 to 1-34, etc., in general formula (1), A １ However, it is a group represented by formula (A-3), or a hydrogen atom, and A ２ However, when the group is represented by equation (A-3), it is shown that the response speed and the electric field strength dependence of the quantum efficiency are superior.

[0171] [Test Y] Next, in addition to the specific compound or comparative compound, a photoelectric conversion element is fabricated using a dye other than the specific compound, and the quantum efficiency, response speed, electric field strength dependence of the quantum efficiency, and manufacturability of the photoelectric conversion element at a wavelength of 570 nm are evaluated by the following method.

[0172] <Fabrication of Photoelectric Conversion Elements> Any specific compound selected from compounds (1-1) to (1-26), compounds (2-1) to (2-3), and compounds (3-1) to (3-12), or each comparative compound, n-type organic semiconductor (fullerene (C) ６０ A photoelectric conversion film 12 is formed by co-depositing a p-type organic semiconductor (compound (P-1)) and one of the dyes selected from (B-1) to (B-17) shown below using vacuum deposition, such that the ratio of the specific compound:dye:p-type organic semiconductor:n-type organic semiconductor is 1:1:2:2 on a single-film basis. The photoelectric conversion elements for each example and comparative example are then fabricated using the same procedure as in Test X. As a result, even when a dye other than the specific compound is used in combination, the same results as those for quantum efficiency, response speed, electric field strength dependence of quantum efficiency, and manufacturability described in Table 1 are obtained.

[0173]

[0174] 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 the following general formula (1). In the general formula (1), W represents a divalent group selected from >C=O, >C=S, >P(=O)R Ｐ１ , >S(=O) ２ , and >S=O. R Ｐ１ represents a hydrogen atom or a substituent. n1 and n2 each independently represent an integer of 0 to 3. m1 and m2 each independently represent an integer of 0 to 2. A １ represents a group represented by formula (A-1), a group represented by formula (A-2), or a hydrogen atom. A ２ represents the group represented by the formula (A-1) or the group represented by the formula (A-2). Ring A and ring B each independently represent a ring structure represented by any one of formulas (D-1) to (D-5). Ring C and ring D each independently represent a ring structure represented by any one of formulas (D-6) to (D-10). However, when both n1 and n2 are 0, at least one of ring C and ring D is a ring structure represented by any one of the formulas (D-6) to (D-8). Ring E and ring F each independently represent a monocyclic aromatic ring group or a 2- to 4-ring condensed conjugated ring group. In the formulas (D-1) to (D-10), Y each independently represents -CR Ｙ１ = or a nitrogen atom. R Ｙ１ represents a hydrogen atom or a substituent. In the formula (D-1), X １ represents a sulfur atom, an oxygen atom, >C=O, >P(=O)R Ｄ１ , >C=S, >S=O, >S(=O) ２ , >CR Ｄ２ R Ｄ３ , >NR Ｄ４ , a selenium atom, a tellurium atom, >SiR Ｄ５ R Ｄ６ , >GeR Ｄ７ R Ｄ８ , or >P(=S)R Ｄ９ . R Ｄ１ to R Ｄ９ each independently represent a hydrogen atom or a substituent. In the formula (D-4), V １ represents an oxygen atom, a sulfur atom, or >NR Ｖ１ Represents R Ｖ１ V represents a hydrogen atom or substituent. ２ and V ３ Each of these independently represents a hydrogen atom or a substituent. In formula (D-5), V ４ is an oxygen atom, a sulfur atom or >NR Ｖ１ Represents R Ｖ１ V represents a hydrogen atom or substituent. ５ X represents an oxygen atom or a sulfur atom. In formulas (D-6) to (D-8), X ２ These are, independently, a sulfur atom, an oxygen atom, and >NR Ｄ１０ R represents a selenium atom or a tellurium atom. Ｄ１０ R represents a hydrogen atom or substituent. In formula (A-1), R １ Cy represents a hydrogen atom or substituent. １ This represents a ring containing two or more carbon atoms, which may have substituents. Q １ This consists of 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 -C(=O)OR Ｑ４ , -C(=O)R Ｑ５ , -S(=O)R Ｑ６ , or -S (=O) ２ R Ｑ７ Represents R Ｑ４ ~R Ｑ７ Each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. In formula (A-2), R ２ R represents a hydrogen atom or substituent. ｂ１ and R ｂ２ These are, independently, a cyano group and -C(=O)OR ｂ３ , -C(=O)R ｂ４ , -S(=O)R ｂ５ , or -S (=O) ２ R ｂ６ Represents R ｂ３ ~R ｂ６ Each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. In formulas (D-1) to (D-10) and (A-1) to (A-2), * and *b represent bond positions, and when ring C represents a ring structure represented by any of formulas (D-6) to (D-10), *b in formulas (D-6) to (D-10) is A １ The bond position on the side is represented, and when ring D represents a ring structure represented by any of the formulas (D-6) to (D-10), *b in formulas (D-6) to (D-10) is A ２ This indicates the bond position on the side. However, compounds represented by general formula (1) do not contain any carboxyl group, salt of a carboxyl group, sulfonic acid group, salt of a sulfonic acid group, phosphate group, salt of a phosphate group, sulfinic acid group, or salt of a sulfinic acid group.

2. The photoelectric conversion element according to claim 1, wherein n1 and n2 are each independently 0 or 1.

3. The photoelectric conversion element according to claim 1, wherein ring A and ring B are each independently ring structures represented by any of the formulas (D-1) to (D-3).

4. The photoelectric conversion element according to claim 1, wherein ring C and ring D are each independently a ring structure represented by formula (D-6) or formula (D-9).

5. A １ The photoelectric conversion element according to claim 1, wherein the base is represented by formula (A-1) or formula (A-2).

6. A １ The photoelectric conversion element according to claim 1, wherein the base is represented by formula (A-1) or formula (A-2), and both m1 and m2 are 0.

7. W is >C=O, or >P(=O)R Ｐ１ The photoelectric conversion element according to claim 1.

8. A １ However, it is a group represented by the above formula (A-1), or a hydrogen atom, and A ２ The photoelectric conversion element according to any one of claims 1 to 7, wherein the base is represented by formula (A-1).

9. A １ However, it is a group represented by formula (A-3), or a hydrogen atom, and A ２ The photoelectric conversion element according to any one of claims 1 to 7, wherein the base is represented by formula (A-3). In formula (A-3), R １ And *b is R in formula (A-1) above. １ This is synonymous with *b. ２ This represents a ring containing three or more carbon atoms, which may have substituents. 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 represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ｑ２ and R ｑ３ These are, independently, a cyano group and -C(=O)OR ｑ４ , -C(=O)R ｑ５ , -S(=O)R ｑ６ , or -S (=O) ２ 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.

10. The photoelectric conversion element according to any one of claims 1 to 7, wherein the photoelectric conversion film further comprises an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed in a state in which the compound represented by the general formula (1) and the n-type organic semiconductor are mixed.

11. The photoelectric element according to claim 10, wherein the n-type organic semiconductor comprises fullerenes selected from the group consisting of fullerenes and their derivatives.

12. The photoelectric conversion element according to any one of claims 1 to 7, wherein the photoelectric conversion film further comprises a p-type organic semiconductor.

13. The photoelectric conversion element according to any one of claims 1 to 7, wherein the photoelectric conversion film further comprises a dye.

14. A photoelectric conversion element according to any one of claims 1 to 7, 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.

15. An image sensor having a photoelectric conversion element according to any one of claims 1 to 7.

16. A light sensor having a photoelectric conversion element according to any one of claims 1 to 7.

17. A method for manufacturing an image sensor, comprising a step of manufacturing a photoelectric conversion element according to any one of claims 1 to 7.

18. A compound represented by the following general formula (1). In the general formula (1), W represents a divalent group selected from >C=O, >C=S, >P(=O)R Ｐ１ , >S(=O) ２ , and >S=O. R Ｐ１ represents a hydrogen atom or a substituent. n1 and n2 each independently represent an integer of 0 to 3. m1 and m2 each independently represent an integer of 0 to 2. A １ represents a group represented by formula (A-1), a group represented by formula (A-2), or a hydrogen atom. A ２ represents the group represented by the formula (A-1) or the group represented by the formula (A-2). Ring A and ring B each independently represent a ring structure represented by any one of formulas (D-1) to (D-5). Ring C and ring D each independently represent a ring structure represented by any one of formulas (D-6) to (D-10). However, when both n1 and n2 are 0, at least one of ring C and ring D is a ring structure represented by any one of the formulas (D-6) to (D-8). Ring E and ring F each independently represent a monocyclic aromatic ring group or a condensed ring conjugated ring group of 2 to 4 rings. In the formulas (D-1) to (D-10), Y each independently represents -CR Ｙ１ = or a nitrogen atom. R Ｙ１ represents a hydrogen atom or a substituent. In the formula (D-1), X １ represents a sulfur atom, an oxygen atom, >C=O, >P(=O)R Ｄ１ , >C=S, >S=O, >S(=O) ２ , >CR Ｄ２ R Ｄ３ , >NR Ｄ４ , a selenium atom, a tellurium atom, >SiR Ｄ５ R Ｄ６ , >GeR Ｄ７ R Ｄ８ , or >P(=S)R Ｄ９ represents. R Ｄ１ to R Ｄ９ each independently represent a hydrogen atom or a substituent. In the formula (D-4), V １ represents an oxygen atom, a sulfur atom or >NR Ｖ１ . R Ｖ１ represents a hydrogen atom or a substituent. V ２ and V ３ Each of these independently represents a hydrogen atom or a substituent. In formula (D-5), V ４ is an oxygen atom, a sulfur atom or >NR Ｖ１ Represents R Ｖ１ V represents a hydrogen atom or substituent. ５ X represents an oxygen atom or a sulfur atom. In formulas (D-6) to (D-8), X ２ These are, independently, a sulfur atom, an oxygen atom, and >NR Ｄ１０ R represents a selenium atom or a tellurium atom. Ｄ１０ R represents a hydrogen atom or substituent. In formula (A-1), R １ Cy represents a hydrogen atom or substituent. １ This represents a ring containing two or more carbon atoms, which may have substituents. Q １ This consists of 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 -C(=O)OR Ｑ４ , -C(=O)R Ｑ５ , -S(=O)R Ｑ６ , or -S (=O) ２ R Ｑ７ Represents R Ｑ４ ~R Ｑ７ Each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. In formula (A-2), R ２ R represents a hydrogen atom or substituent. ｂ１ and R ｂ２ These are, independently, a cyano group and -C(=O)OR ｂ３ , -C(=O)R ｂ４ , -S(=O)R ｂ５ , or -S (=O) ２ R ｂ６ Represents R ｂ３ ~R ｂ６ Each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. In formulas (D-1) to (D-10) and (A-1) to (A-2), * and *b represent bond positions, and when ring C represents a ring structure represented by any of formulas (D-6) to (D-10), *b in formulas (D-6) to (D-10) is A １ The bond position on the side is represented, and when ring D represents a ring structure represented by any of the formulas (D-6) to (D-10), *b in formulas (D-6) to (D-10) is A ２ This indicates the bond position on the side. However, compounds represented by general formula (1) do not contain any carboxyl group, salt of a carboxyl group, sulfonic acid group, salt of a sulfonic acid group, phosphate group, salt of a phosphate group, sulfinic acid group, or salt of a sulfinic acid group.

19. The compound according to claim 18, wherein n1 and n2 are each independently 0 or 1.

20. The compound according to claim 18, wherein ring A and ring B are each independently ring structures represented by any of the formulas (D-1) to (D-3).

21. The compound according to claim 18, wherein ring C and ring D are each independently a ring structure represented by formula (D-6) or formula (D-9).

22. A １ The compound according to claim 18, wherein the group is represented by formula (A-1) or formula (A-2).

23. A １ The compound according to claim 18, wherein the group is represented by formula (A-1) or formula (A-2), and both m1 and m2 are 0.

24. W is >C=O, or >P(=O)R Ｐ１ The compound according to claim 18.

25. A １ However, it is a group represented by the above formula (A-1), or a hydrogen atom, and A ２ The compound according to any one of claims 18 to 24, wherein the group is represented by the formula (A-1).

26. A １ However, it is a group represented by formula (A-3), or a hydrogen atom, and A ２ The compound according to any one of claims 18 to 24, wherein the group is represented by formula (A-3). In formula (A-3), R １ And *b is R in formula (A-1) above. １ This is synonymous with *b. ２ This represents a ring containing three or more carbon atoms, which may have substituents. 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 represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ｑ２ and R ｑ３ These are, independently, a cyano group and -C(=O)OR ｑ４ , -C(=O)R ｑ５ , -S(=O)R ｑ６ , or -S (=O) ２ 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.

Images