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

Abstract

The present invention addresses the problem of providing a photoelectric conversion element of which the quantum efficiency is less dependent on the electric field intensity when green / red light is received. A photoelectric conversion element according to the present invention comprises a conductive film, a photoelectric conversion film, and a transparent conductive film, in the stated order. The photoelectric conversion film contains a compound represented by 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 photoelectric conversion device containing a dye compound with a specific structure.

[0003] Japanese Patent Publication No. 2003-007360

[0004] With the increasing demand for improved performance in image sensors and optical sensors, there is a need for photoelectric conversion elements that exhibit superior characteristics. One characteristic required of a photoelectric conversion element is that its quantum efficiency does not change significantly when the electric field strength is changed; in other words, its quantum efficiency has low dependence on electric field strength. Under these requirements, the present inventors fabricated and investigated a photoelectric conversion element containing the compound disclosed in Patent Document 1. They found that the dependence of the quantum efficiency on electric field strength when receiving green-red light did not meet the desired level, indicating room for improvement. The green-red light referred to above is light with a wavelength of 500 to 780 nm.

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

[0006] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in that order, wherein the photoelectric conversion film contains a compound represented by formula (1) described later. [2] The photoelectric conversion element according to [1], wherein the compound represented by formula (1) is a compound represented by formula (2) described later. [3] X ２１ and X ２４ The photoelectric conversion element described in [2], wherein the element is a nitrogen atom. [4] R５ and R ６ A photoelectric conversion element according to [2] or [3], wherein at least one of the members is a group represented by formula (B-1) described later. [5] A photoelectric conversion element according to any one of [1] to [4], wherein the compound represented by formula (1) is a compound represented by formula (3) described later. [6] R ７ and R ８ [5] A photoelectric element according to any one of [1] to [6], wherein A is a group represented by formula (A-3) described later or a group represented by formula (A-4) described later. [8] A photoelectric element according to any one of [1] to [7], wherein A is a group represented by formula (A-5) described later, a group represented by formula (A-6) described later, or a group represented by formula (A-7) described later. [9] A photoelectric element according to any one of [1] to [8], wherein the photoelectric conversion film further comprises an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed when the compound represented by formula (1) and the n-type organic semiconductor are mixed.

[10] A photoelectric element according to [9], wherein the n-type organic semiconductor comprises fullerenes selected from the group consisting of fullerenes and their derivatives.

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

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

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

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

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

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

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

[13] .

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

[13] .

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

[13] .

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

[18] The compound according to

[17] , which is a compound represented by formula (2) described later.

[19] X ２１ and X ２４ The compound described in

[18] , wherein is a nitrogen atom.

[20] R５ and R ６ At least one of which is a group represented by the following formula (B-1), the compound according to

[18] or

[19] .

[21] The compound according to

[17] , which is a compound represented by the following formula (3).

[22] R ７ and R ８ are different groups from each other, the compound according to

[21] .

[23] A is a group represented by the following formula (A-3) or a group represented by the following formula (A-4), the compound according to any one of

[17] to

[22] .

[24] A is a group represented by the following formula (A-5), a group represented by the following formula (A-6), or a group represented by the following formula (A-7), the compound according to any one of

[17] to

[23] .

[0008] According to the present invention, a photoelectric conversion device with a small electric field strength dependence of the quantum efficiency when receiving green-red light can be provided. Further, according to the present invention, an imaging device, an optical sensor, a method for manufacturing an imaging device, and a compound related to the above photoelectric conversion device can also be provided.

[0009] It is a cross-sectional schematic view showing a configuration example of a photoelectric conversion device. It is a cross-sectional schematic view showing a configuration example of a photoelectric conversion device.

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

[0011] In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0012] In this specification, a hydrogen atom may be either a light hydrogen atom (ordinary hydrogen atom) or a heavy hydrogen atom (for example, a deuterium atom, etc.). In this specification, when there are a plurality of substituents and linking groups (hereinafter also referred to as "substituents, etc.") represented by specific symbols, or when a plurality of substituents, etc. are defined simultaneously, it means that each substituent, etc. may be the same as or different from each other. This also applies to the definition 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: phosphate group, salt of phosphate group, 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 formula (1) (hereinafter also referred to as the "specific compound").

[0027] The reason why a photoelectric conversion element having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is still within the scope of the present invention. There are cases where it is necessary to design a so-called DA-type dye having a donor portion and an acceptor portion to have absorption in the long-wavelength range (for example, the wavelength range of green-red light). One design concept for lengthening the absorption wavelength of a compound is to increase the number of fused aromatic rings, but in addition to the increase in conjugation length, aggregation can increase excessively due to actions such as π-π stacking. The specific compound of the present invention achieves lengthening the absorption wavelength by expanding the double bond at the bonding position of the donor portion and acceptor portion of the DA-type dye, and such a compound can also suppress the increase in aggregation. Furthermore, the specific compound does not contain predetermined acid groups, etc., and has a specific donor structure and acceptor structure, so electron trapping due to dipole moment is also suppressed. As described above, because aggregation and electron trapping of specific compounds within the photoelectric conversion film are suppressed, efficient charge separation can be achieved even at low electric field strengths. As a result, the dependence of the quantum efficiency of the photoelectric conversion element on electric field strength when receiving green-red light is considered to be small. Hereinafter, a smaller dependence on electric field strength when receiving green-red light 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 ７ It 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 specific compounds, which are compounds represented by formula (1).

[0032]

[0033] In formula (1), R １ , R ２ , R ３ , R ４ , and R ５ Each of these independently represents a hydrogen atom or a substituent. X is -NR Ｘ１ - or -C (R Ｘ２ ) (Caution Ｘ３ ) represents R Ｘ１ R represents a hydrogen atom or substituent. Ｘ２ and R Ｘ３ Each of these independently represents a substituent. However, if X is -C(R) Ｘ２ ) (Caution Ｘ３ ) - When representing R Ｘ２ and R Ｘ３ At least one of them represents a substituent with 2 or more carbon atoms, or R Ｘ２ and R Ｘ３ These elements are bonded to each other to form a ring which may have substituents. B represents an aromatic ring which may have substituents. However, X is -NR Ｘ１ When represented by -, B represents an aromatic heterocycle which may have substituents. A represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (A-1), C represents a ring which contains two or more carbon atoms and may have substituents. Y ａ１１ This consists of an oxygen atom, a sulfur atom, and =NR ａ１１ , or =CR ａ１１ R ａ１２ Represents R ａ１１ R represents a hydrogen atom or substituent. ａ１２ and R ａ１３ These are, independently, a cyano group and -SO ２ R ａ１４ , -COOR ａ１５ , or -COR ａ１６ Represents R ａ１４ , R ａ１５ , and R ａ１６Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ１２ is -O-, -NR ａ１７ -, -N=, -C(R ａ１８ ) (Caution ａ１９ )-,-CR ａ２０ = or -C (=Y ａ１３ ) represents R ａ１７ , R ａ１８ , R ａ１９ , and R ａ２０ Each of these independently represents a hydrogen atom or a substituent. ａ１３ is an oxygen atom, a sulfur atom, =NR ａ２７ , or =CR ａ２８ R ａ２９ Represents R ａ２７ , R ａ２８ , and R ａ２９ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position. In formula (A-2), R ａ２１ and R ａ２２ These are, independently, a cyano group and a -COOR group. ａ２３ , -COR ａ２４ , -CSOR ａ２５ , or -CSR ａ２６ Represents R ａ２３ , R ａ２４ , R ａ２５ , and R ａ２６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. However, the compound represented by formula (1) does not contain any carboxylic acid group and its salts, sulfonic acid group and its salts, or hydroxamic acid group and its salts.

[0034] In formula (1), R １ , R ２ , R ３ , R ４ , and R ５ Each of these independently represents a hydrogen atom or a substituent. Examples of the substituents include the substituent W mentioned above. １ , R２ , R ３ , and R ４ are preferably hydrogen atoms in that the effects of the present invention are more excellent. R ５ is preferably a substituent in that the effects of the present invention are more excellent, and more preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

[0035] R ５ The above-mentioned aliphatic hydrocarbon group represented by may be linear, branched, or cyclic, and is preferably branched or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, and an alkyl group is preferred. The number of carbon atoms of the linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 4, and particularly preferably 1 or 2. The number of carbon atoms of the branched aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, still 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 of the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, still more preferably 3 to 6. As described above, the aliphatic hydrocarbon group may have a substituent. Examples of the substituent include the above-mentioned substituent W, and a halogen atom, a silyl group, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or an alkoxy group which may have a substituent are preferred. Preferred embodiments of the above-mentioned halogen atom, silyl group, aromatic ring group which may have a substituent, aliphatic heterocyclic group which may have a substituent, or alkoxy group which may have a substituent are the same as the groups represented by R ｂ１１ in the formula (B-1) described later.

[0036] Among the above-mentioned aliphatic hydrocarbon groups which may have a substituent, a group represented by -C(R Ｌ１１ )(R Ｌ１２ )(R Ｌ１３ ) is preferred. R Ｌ１１ , R Ｌ１２ , and R Ｌ１３Each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. However, R Ｌ１１ , R Ｌ１２ , and R Ｌ１３ at least two of which represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. Examples of the substituent which the above alkyl group and aromatic ring group may have include the above-described substituent W, and an alkyl group, an aryl group, or a halogen atom is preferable. The alkyl group represented by R Ｌ１１ to R Ｌ１３ may be linear, branched, or cyclic. The number of carbon atoms of the above alkyl group is preferably 1 to 6, more preferably 1 to 3. The definition and preferred embodiments of the aromatic ring group represented by R Ｌ１１ , R Ｌ１２ , and R Ｌ１３ are the same as those of the aromatic ring group represented by R １ , R ２ , R ３ , R ４ , and R ５ .

[0037] The alkyl group which may have a substituent and the aromatic ring group which may have a substituent represented by R Ｌ１１ to R Ｌ１３ may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. Examples of the divalent linking group include a divalent hydrocarbon group (for example, an alkylene group or an arylene group), -O-, -CO-, -SO ２ -, -NH-, and groups formed by combining these. As the above ring, a non-aromatic ring is preferable. Also, the above ring may be either a monocyclic ring or a polycyclic ring. The number of ring atoms of the above ring is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. The above ring may have a hetero atom. Examples of the above hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferable. Examples of the substituent which the above ring may have include the above-described substituent W, and an alkyl group, an aryl group, or a halogen atom is preferable.

[0038] R ５ The aromatic ring group represented above may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic ring group may be monocyclic or polycyclic, with monocyclic being preferred. The number of ring member atoms of the aromatic ring group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 to 8. The definition and specific examples of an 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 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 an aromatic heterocyclic group are as described above, with a thiophene ring group, a furan ring group, or a pyridine ring group being preferred. As described above, the aromatic ring group may have substituents, and it is preferable that it has substituents in that the effects of the present invention are better. Preferred substituents are halogen atoms, silyl groups, optionally substituted aliphatic hydrocarbon groups, optionally substituted aromatic ring groups, optionally substituted aliphatic heterocyclic groups, or optionally substituted alkoxy groups, with halogen atoms, silyl groups, or alkyl groups being more preferred. Preferred embodiments of the halogen atom, silyl group, optionally substituted aliphatic hydrocarbon group, optionally substituted aromatic ring group, optionally substituted aliphatic heterocyclic group, or optionally substituted alkoxy group are as follows in formula (B-1) described later, R ｂ１１ These are the same as each group represented by . If the above aromatic ring group has substituents, the number is not particularly limited, but 1 to 3 is preferred.

[0039] R ５The aliphatic heterocyclic group represented above may be monocyclic or polycyclic, with monocyclic being preferred. The number of ring member atoms of the aliphatic heterocyclic group is preferably 3 to 18, more preferably 5 to 10, and even more preferably 5 to 8. Examples of heteroatoms that the aliphatic heterocyclic group may have 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 aliphatic heterocyclic group are as described above, with thiolane rings, piperidine rings, tetrahydrofuran rings, or tetrahydropyran rings being preferred. As described above, the aliphatic heterocyclic group may have substituents. Preferred embodiments of the substituents are the same as those that may be present on the aromatic ring. If the aliphatic heterocyclic group has substituents, the number is not particularly limited, but 1 to 3 is preferred.

[0040] In particular, X is -NR Ｘ１ - If R ５ As the substituent represented above, the group represented by formula (B-1) is preferred.

[0041]

[0042] In formula (B-1), D represents a ring containing two or more carbon atoms, which may have substituents. The two carbon atoms contained in D are the two carbon atoms explicitly shown in formula (B-1). The ring may be either an aromatic ring or a non-aromatic ring, with an aromatic ring being preferred. The ring may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. The number of carbon atoms in the ring is two or more, preferably 3 to 10, more preferably 4 to 10, and even more preferably 5 or 6. The ring may contain heteroatoms. Examples of heteroatoms include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen atoms being preferred. The ring represented by D is R ｂ１１ It may have a different substituent. ｂ１１ Examples of substituents other than those mentioned above include substituent W, and preferred embodiments are described later as R. ｂ１１ It is the same as R. ｂ１１The number of substituents other than the one specified is preferably 1 to 3, and more preferably 1 or 2.

[0043] In formula (B-1), R ｂ１１ This represents a halogen atom, a silyl group, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted alkoxy group. Examples of substituents that the above aliphatic hydrocarbon group, aromatic ring group, aliphatic hydrocarbon group, and alkoxy group may have include the substituent W described above, and is preferably an aliphatic hydrocarbon group (preferably having 1 to 4 carbon atoms), an aromatic ring group (preferably having 5 to 10 ring member atoms), a halogen atom, a silyl group, an optionally substituted aromatic heterocyclic group (preferably having 3 to 10 ring member atoms), or an alkoxy group (preferably having 1 to 4 carbon atoms), and more preferably an alkyl group (preferably having 1 to 3 carbon atoms) or a halogen atom.

[0044] The above silyl group is -SiR Ｓｉ ３ It is a group represented by R. Ｓｉ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. Ｓｉ The definitions and preferred embodiments of an optionally substituted aliphatic hydrocarbon group, optionally substituted aromatic ring group, and optionally substituted aliphatic heterocyclic group are as follows: ｂ１１ This is the same as an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, and an optionally substituted aliphatic heterocyclic group represented by .

[0045] R ｂ１１The aliphatic hydrocarbon group represented above may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The 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 to 3. 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.

[0046] R ｂ１１ The above definitions and preferred embodiments of aromatic ring groups and aliphatic heterocyclic groups represented by R ５ These are the same as aromatic ring groups and aliphatic heterocyclic groups represented by .

[0047] The alkyl group of the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3.

[0048] In formula (B-1), * indicates the bonding position.

[0049] In equation (1), X is -NR Ｘ１ - or -C (R Ｘ２ ) (Caution Ｘ３ )- represents the fact that the effects of the present invention are superior, -NR Ｘ１ - is preferable.

[0050] R Ｘ１ R represents a hydrogen atom or substituent. Ｘ１ The definition and preferred embodiment of the substituent represented by R ５ The definition and preferred embodiment of the substituent represented by are the same as those shown. X is -NR Ｘ１ - In this case, the effects of the present invention are superior, R ５ and R Ｘ１ At least one of them is preferably a group represented by the above formula (B-1), and R ５ and R Ｘ１It is more preferable that the group is represented by formula (B-1).

[0051] R Ｘ２ and R Ｘ３ Each of these independently represents a substituent. Ｘ２ and R Ｘ３ Examples of substituents represented by the above-mentioned substituent W include an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group, with an optionally substituted aliphatic hydrocarbon group being more preferred. The definition and preferred embodiments of the optionally substituted aliphatic hydrocarbon group, optionally substituted aromatic ring group, or optionally substituted aliphatic heterocyclic group are given by R ５ This is the same as an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group represented by .

[0052] However, R Ｘ２ and R Ｘ３ At least one of them represents a substituent with 2 or more carbon atoms, or R Ｘ２ and R Ｘ３ These atoms bond to each other to form a ring which may have substituents. Examples of substituents having two or more carbon atoms include groups with two or more carbon atoms from among the substituents mentioned above (for example, aliphatic hydrocarbon groups with two or more carbon atoms and aromatic ring groups with two or more carbon atoms). Note that the carbon number of the substituent refers to the total carbon number of the substituent. For example, R Ｘ２ If the substituent is an ethyl group having a methoxy group, then the number of carbon atoms is 3. Ｘ２ and R Ｘ３The ring formed by the bonding of these elements may be either an aromatic ring or a non-aromatic ring, with non-aromatic rings being preferred. The ring may also be monocyclic or polycyclic. The number of ring member atoms in the ring is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. The ring may have heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, nitrogen, or oxygen atoms being preferred. Examples of substituents that the ring may have include the substituent W mentioned above, with alkyl groups, aryl groups, or halogen atoms being preferred.

[0053] In terms of having superior effects, R Ｘ２ and R Ｘ３ It is also preferable that these groups be different from each other.

[0054] In formula (1), B represents an aromatic ring which may have substituents. X is -NR Ｘ１ When represented by -, B represents an aromatic heterocycle which may have substituents. X is -C(R Ｘ２ ) (Caution Ｘ３ When ) is expressed as , B may be either an aromatic heterocycle having substituents or an aromatic hydrocarbon ring having substituents, with the aromatic hydrocarbon ring having substituents being preferred. In this specification, an aromatic heterocycle is intended to be an aromatic ring containing at least one heteroatom as a ring member atom. Also, for example, when a carbonyl group (-C(=O)-) is included as part of the ring, the carbon atom is a ring member atom, but the oxygen atom is not included as a ring member atom, for example, benzoquinone is not included in the heterocycle. The aromatic ring may be monocyclic or polycyclic. The number of ring member atoms of the aromatic ring is preferably 5 to 20, and more preferably 6 to 14. The aromatic ring may also be a monocyclic 6-membered ring or a fused ring containing a 6-membered ring. The heteroatom included in the aromatic heterocycle is preferably a sulfur atom, a nitrogen atom, or an oxygen atom, and more preferably a nitrogen atom.

[0055] The substituents that the aromatic ring may have include optionally substituted aliphatic hydrocarbon groups, optionally substituted aromatic ring groups, optionally substituted aliphatic heterocyclic groups, optionally substituted alkoxy groups, halogen atoms, and silyl groups, with optionally substituted aliphatic hydrocarbon groups, optionally substituted alkoxy groups, or halogen atoms being preferred. The definitions and preferred embodiments of each of the groups exemplified as substituents are given in R in formula (B-1) above. ｂ１１ These are the same as each of the groups represented by .

[0056] In formula (1), A represents a group represented by formula (A-1) or formula (A-2). The group represented by formula (A-3) or formula (A-4) is preferred in terms of superior effects of the present invention, and the group represented by formula (A-5), formula (A-6), or formula (A-7) is more preferred. Formulas (A-1) to (A-7) will be described later.

[0057] The specific compounds include carboxylic acid groups (-COOH) and their salts, and sulfonic acid groups (-SO). ３ It does not contain H) or its salts, nor a hydroxamic acid group (-CO-NH-OH) or its salts. The form of the salt is not particularly limited, and examples include metal salts and ammonium salts.

[0058] The specific compound is preferably a compound represented by formula (2) or formula (3), and more preferably a compound represented by formula (2), in that the effects of the present invention are superior.

[0059]

[0060] In formula (2), R １ , R ２ , R ３ , R ４ , R ５ , and A are R in equation (1) １ , R ２ , R ３ , R ４ , R ５ It is synonymous with A.

[0061] In formula (2), R ６R represents a hydrogen atom or a substituent, and substituents are preferred. ６ The definition and preferred embodiment of the group represented by formula (1) is R Ｘ１ It is the same as the group represented by . The present invention has superior effects, R ５ and R ６ Preferably, at least one of them is a group represented by the above formula (B-1), and R ５ and R ６ It is more preferable that the group is represented by the formula (B-1) described above.

[0062] In formula (2), X ２１ , X ２２ , X ２３ , and X ２４ Each of these is independently -CR ２１ = or represents a nitrogen atom. However, X ２１ , X ２２ , X ２３ , and X ２４ At least one of them represents a nitrogen atom. In terms of the advantages of the present invention, X ２１ and X ２４ Preferably, at least one of them is a nitrogen atom, X ２１ and X ２４ It is more preferable that X is a nitrogen atom. ２１ and X ２４ X is a nitrogen atom, ２２ and X ２３ ga-CR ２１ It is even more preferable that they are equal. ２１ represents a hydrogen atom or a substituent. Examples of the substituents include substituents that may be present on the aromatic ring represented by B in formula (2), and the preferred embodiments are the same.

[0063] X ２１ , X ２２ , X ２３ , and X ２４ Two of the adjacent ones are -CR ２１ When representing =, two adjacent -CR ２１ = R inside ２１ These elements may be bonded to each other to form a ring which may have substituents. For example, X ２２ and X ２３ ga-CR ２１When representing =, X ２２ R inside ２１ and X ２３ R inside ２１ They may be bonded to each other to form a ring which may have substituents. ２１ and X ２２ , and, X ２３ and X ２４ The same applies to the above. The above ring may be monocyclic or polycyclic. The number of ring member atoms of the above ring is preferably 4 to 14, more preferably 5 to 10, and even more preferably 6 to 10. The above ring may be either an aromatic ring or an aliphatic ring, with an aromatic ring being preferred. Also, if the above ring is polycyclic, it may be a fused ring of an aromatic ring and an aliphatic ring. The above ring may have heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, oxygen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms, with sulfur atoms, nitrogen atoms, or oxygen atoms being preferred, and nitrogen atoms being more preferred. The above ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The definitions and preferred embodiments of substituents that the above ring may have are as follows: ２１ This is the same as the substituent represented by .

[0064] However, the compound represented by formula (2) does not contain any carboxylic acid group and its salt, sulfonic acid group and its salt, or hydroxamic acid group and its salt.

[0065] In formula (3), R １ , R ２ , R ３ , R ４ , R ５ , and A are R in equation (1) １ , R ２ , R ３ , R ４ , R ５ It is synonymous with A.

[0066] In formula (3), R ７ and R ８ R represents a substituent. ７ and R ８ The definition and preferred embodiment of the substituent represented by formula (1) is R Ｘ２ and R Ｘ３It is the same as the group represented by , where R ７ and R ８ At least one of them represents a substituent with 2 or more carbon atoms, or R ７ and R ８ These elements bond to each other to form a ring which may have substituents. ７ and R ８ The definition and preferred embodiment of a ring which may have substituents formed by the bonding of R Ｘ２ and R Ｘ３ This is the same as a ring which may have substituents formed by the bonding of these elements to each other. The present invention offers superior effects, R ７ and R ８ It is also preferable that these groups be different from each other.

[0067] In formula (3), X ３１ , X ３２ , X ３３ , and X ３４ Each of these is independently -CR ３１ = or represents a nitrogen atom, -CR ３１ = is preferable. R ３１ represents a hydrogen atom or a substituent. Examples of the substituents include substituents that may be present on the aromatic ring represented by B in formula (2), and the preferred embodiments are the same.

[0068] X ３１ , X ３２ , X ３３ , and X ３４ Two of the adjacent ones are -CR ３１ When representing =, two adjacent -CR ３１ = R inside ３１ These elements may be bonded to each other to form a ring which may have substituents. For example, X ３２ and X ３３ ga-CR ３１ When representing =, X ３２ R inside ３１ and X ３３ R inside ３１ They may be bonded to each other to form a ring which may have substituents. ３１ and X ３２ , X ３３ and X ３４The same applies to R. The above ring may be monocyclic or polycyclic. The number of ring member atoms of the above ring is preferably 4 to 14, more preferably 5 to 10, and even more preferably 6 to 10. The above ring may be either an aromatic ring or an aliphatic ring, with an aromatic ring being preferred. Furthermore, if the above ring is polycyclic, it may be a fused ring of an aromatic ring and an aliphatic ring. The above ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The definitions and preferred embodiments of substituents that the above ring may have are as follows: ３１ This is the same as the substituent represented by .

[0069] However, the compound represented by formula (3) does not contain any carboxylic acid group and its salt, sulfonic acid group and its salt, or hydroxamic acid group and its salt.

[0070] The groups represented by formula (A-1) and formula (A-2) will be described in detail below.

[0071]

[0072] In formula (A-1), C represents a ring containing two or more carbon atoms, which may have substituents. The two carbon atoms contained in C are the two carbon atoms explicitly stated 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 containing the two carbon atoms explicitly stated 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 contain heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with nitrogen or oxygen being preferred. The number of heteroatoms in the above ring is preferably 0 to 10, and more preferably 0 to 5. Among the carbon atoms constituting the ring represented by C above, the carbon atoms at the bond positions marked with * in formula (A-1) and Y ａ１１Carbon atoms other than those bonded to the carbon atom may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S). However, it is preferable that the carbonyl carbons and thiocarbonyl carbons are not adjacent to each other. In other words, it is preferable that the carbonyl group and thiocarbonyl group are not adjacent to each other in the above ring.

[0073] 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.

[0074] 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.

[0075] In formula (A-1), Y ａ１１ is an oxygen atom, a sulfur atom, =NR ａ１１ , or =CR ａ１１ R ａ１２ 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. ａ１１ represents a hydrogen atom or a substituent. Examples of substituents include the substituent W mentioned 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. 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 above aliphatic heterocyclic group are a sulfur atom, an oxygen atom, or a nitrogen atom. ａ１１ Examples of substituents that each group represented by the above substituent W may have include the substituents exemplified by substituent W. ａ１２ and R ａ１３ These are, independently, a cyano group and -SO ２ R ａ１４ , -COOR ａ１５ , or -COR ａ１６ Represents R ａ１４ , R ａ１５ , and R ａ１６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ１４ , R ａ１５ , and R ａ１６ The definitions and preferred embodiments of each group represented by R ａ１１ These substituents are the same as those exemplified.

[0076] In formula (A-1), Y ａ１２ is -O-, -NR ａ１７ -, -N=, -C(R ａ１８ ) (Caution ａ１９ )-,-CR ａ２０ = or -C (=Y ａ１３ ) represents -C(=Y ａ１３ ) - is preferable. R ａ１７ , R ａ１８ , R ａ１９ , and R ａ２０ Each of these independently represents a hydrogen atom or a substituent. Examples of substituents include the substituent W described above, and preferred substituents are an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group, and a cyano group. ａ１７ , R ａ１８ , R ａ１９ , and R ａ２０ The definitions and preferred embodiments of an aliphatic hydrocarbon group which may have substituents represented by R ａ１１ The substituents represented are the same as those exemplified. ａ１３ is an oxygen atom, a sulfur atom, =NR ａ２７ , or =CR ａ２８ R ａ２９ 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. ａ２７ , R ａ２８ , and R ａ２９ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, and an optionally substituted aliphatic heterocyclic group. ａ２７ , R ａ２８ , and R ａ２９ The definition and preferred embodiment are, respectively, R ａ１１ , R ａ１２ , and R ａ１３ It is the same as this.

[0077] In equation (A-1), * indicates the bonding position.

[0078] In formula (A-2), R ａ２１ and Rａ２２ These are, independently, a cyano group and a -COOR group. ａ２３ , -COR ａ２４ , -CSOR ａ２５ , or -CSR ａ２６ This represents the superior effect of the present invention, R ａ２１ and R ａ２２ Preferably, at least one of them is a cyano group, R ａ２１ and R ａ２２ It is more preferable that it is a cyano group. ａ２３ , R ａ２４ , R ａ２５ , and R ａ２６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ２３ , R ａ２４ , R ａ２５ , and R ａ２６ The definitions and preferred embodiments of each group represented by R ａ１４ , R ａ１５ , and R ａ１６ It is the same as the base represented by .

[0079] The group represented by formula (A-1) is preferred over the group represented by formula (A-3) in terms of superior effects of the present invention. Furthermore, the group represented by formula (A-2) is preferred over the group represented by formula (A-4) in terms of superior effects of the present invention.

[0080]

[0081] In formula (A-3), Y ａ３１ and Y ａ３２ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ３１ , or =CR ａ３２ R ａ３３ Represents R ａ３１ R represents a hydrogen atom or substituent. ａ３２ and R ａ３３ These are, independently, a cyano group and -SO ２ R ａ３４ , -COOR ａ３５ , or -COR ａ３６ Represents R ａ３４ , R ａ３５ , and R ａ３６Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ３１ and Y ａ３２ The definition and preferred embodiment of the base represented by formula (A-1) is Y ａ１１ It is the same as the group represented by R. ａ３１ , R ａ３２ , R ａ３３ , R ａ３４ , R ａ３５ , and R ａ３６ The definition and preferred embodiment of the group represented by formula (A-1) are, respectively, R ａ１１ , R ａ１２ , R ａ１３ , R ａ１４ , R ａ１５ , and R ａ１６ It is the same as this.

[0082] In formula (A-3), E represents a ring containing three or more carbon atoms, which may have substituents. The three carbon atoms contained in E are the three carbon atoms explicitly stated in formula (A-3). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number containing the three carbon atoms explicitly stated 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 fused ring containing a five-membered ring, a six-membered ring, or at least one of a five-membered ring and a six-membered ring is preferred. The number of carbon atoms in the fused ring containing at least one of a five-membered ring and a six-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may contain 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 in the above ring is preferably 0 to 10, and more preferably 0 to 5. Among the carbon atoms constituting the ring represented by E above, the carbon atoms at the bond positions marked with * in formula (A-3), and Y ａ３１ or Y ａ３２Carbon atoms other than those bonded to may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S). However, in the ring represented by E, it is preferable that carbonyl carbons and thiocarbonyl carbons are not adjacent to each other.

[0083] In formula (A-3), * indicates the bonding position.

[0084] In formula (A-4), R ａ４１ is a cyano group, -COOR ａ４２ , -COR ａ４３ , -CSOR ａ４４ , or -CSR ａ４５ The cyano group is preferred because it represents and provides superior effects of the present invention. ａ４２ , R ａ４３ , R ａ４４ , and R ａ４５ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ４２ , R ａ４３ , R ａ４４ , and R ａ４５ The definition and preferred embodiment of the group represented by formula (A-2) is R ａ２３ , R ａ２４ , R ａ２５ , and R ａ２６ These are the same as each group represented by . * indicates the bond position.

[0085] The group represented by formula (A-1) is more preferably the group represented by formula (A-5) or formula (A-6) 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-7) in terms of superior effects of the present invention.

[0086]

[0087] In formula (A-5), Y ａ５１ , Y ａ５２ , and Y ａ５３ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ５１ , or =CR ａ５２ R ａ５３In 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. ａ５１ and Y ａ５２ It is preferable that it is an oxygen atom, Y ａ５１ , Y ａ５２ , and Y ａ５３ It is more preferable that it is an oxygen atom. ａ５１ R represents a hydrogen atom or substituent. ａ５２ and R ａ５３ These are, independently, a cyano group and -SO ２ R ａ５４ , or -COOR ａ５５ , or -COR ａ５６ Represents R ａ５４ , R ａ５５ , and R ａ５６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ５１ , R ａ５２ , R ａ５３ , R ａ５４ , R ａ５５ , and R ａ５６ The definition and preferred embodiment of the group represented by formula (A-1) are, respectively, R ａ１１ , R ａ１２ , R ａ１３ , R ａ１４ , R ａ１５ , and R ａ１６ It is the same as this.

[0088] In formula (A-5), 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 ａ５８ , and R ａ５９Each 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.

[0089] In equation (A-5), * indicates the bonding position.

[0090] In formula (A-6), Y ａ６１ and Y ａ６２ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ６１ , or =CR ａ６２ R ａ６３ 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. ａ６１ R represents a hydrogen atom or substituent. ａ６２ and R ａ６３ These are, independently, a cyano group and -SO ２ R ａ６４ , -COOR ａ６５ , or -COR ａ６６ Represents R ａ６４ , R ａ６５ , and R ａ６６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ６１ , R ａ６２ , R ａ６３ , R ａ６４ , R ａ６５ , and R ａ６６ The definition and preferred embodiment of the group represented by formula (A-1) are, respectively, R ａ１１ , R ａ１２ , R ａ１３ , R ａ１４ , R ａ１５ , and R ａ１６ It is the same as this.

[0091] In formula (A-6), F represents an aromatic ring containing two or more carbon atoms, which may have substituents. The aromatic ring may be monocyclic or polycyclic. The number of member atoms of the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of member atoms of the aromatic ring is the number including the two carbon atoms explicitly shown in the formula. 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, with 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 being preferred, a benzene ring, naphthalene ring, or thiophene ring being more preferred, and a benzene ring being even more preferred. Examples of substituents that the aromatic ring may have include the group exemplified by substituent W, with alkyl groups or halogen atoms being 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.

[0092] In formula (A-6), * indicates the bonding position.

[0093] In equation (A-7), * indicates the bonding position.

[0094] The following are specific examples of particular compounds, but the present invention is not limited to these. In the examples below, * indicates the bond position with the group represented by A. Me represents a methyl group, and TMS represents a trimethylsilyl group.

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] Specific examples of the group represented by A are shown below. * indicates the bond position. Me represents a methyl group, and Ph represents a phenyl group.

[0111]

[0112]

[0113]

[0114]

[0115] 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 excellent manufacturability.

[0116] The specific compound is preferably one with a single-film ionization potential of -5.0 to -6.0 eV, in terms of stability when used as a p-type organic semiconductor and energy level matching with an n-type organic semiconductor.

[0117] 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.

[0118] The specific compound is particularly useful as a material for photoelectric conversion films used in image sensors, optical sensors, or photocells. The specific compound often functions as a dye within the photoelectric conversion film. Furthermore, the specific compound can also be used as a coloring material, liquid crystal material, organic semiconductor material, charge transport material, pharmaceutical material, and fluorescent diagnostic agent material.

[0119] 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.

[0120] 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.

[0121] <n-type organic semiconductor> The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the specified compounds mentioned above. The n-type organic semiconductor is a compound different from the specified compounds mentioned above. The n-type organic semiconductor is an acceptor organic semiconductor material (compound), and refers to an organic compound that has the property of readily accepting electrons. In other words, the n-type organic semiconductor is the organic compound with the greater electron affinity when two organic compounds are used in contact. In other words, any organic compound that has electron-accepting properties can be used as an acceptor organic semiconductor. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and their derivatives; condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives); and heterocyclic compounds of 5 to 7 membered rings having at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, etc.). ); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid diimide derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and their derivatives; triazole compounds; distylyl arylene derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silole compounds; 3,4,9,10-perylenetetracarboxylic acid dianhydride; 3,4,9,10-perylenetetracarboxylic acid diimide derivatives; and the compounds described in paragraphs

[0056] to

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

[0122] 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.

[0123] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.

[0124] 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.

[0125] 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.

[0126] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or greater.

[0127] 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%.

[0128] 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.

[0129] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness of the specific compound on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the n-type organic semiconductor on a single-layer basis) × 100) is preferably 20 to 80 volume%, and more preferably 40 to 80 volume%. When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (film thickness of the specific compound on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the n-type organic semiconductor on a single-layer basis + film thickness of the p-type organic semiconductor on a single-layer basis) × 100) is preferably 10 to 75 volume%, and more preferably 15 to 50 volume%. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, an n-type organic semiconductor, and a p-type organic semiconductor included as desired. "Substantial" means that the total content of the specific compound, n-type organic semiconductor, and p-type organic semiconductor relative to the total volume of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume.

[0130] <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.

[0131] 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 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. As p-type organic semiconductors, for example, compounds with a smaller ionization potential than n-type organic semiconductors can be used, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are given below.

[0132]

[0133]

[0134]

[0135]

[0136] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or greater.

[0137] The p-type organic semiconductor material 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%.

[0138] 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.

[0139] <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.

[0140] 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.

[0141] 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%.

[0142] <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.

[0143] 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.

[0144] [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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] [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.

[0149] <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.

[0150] 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.

[0151] <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.

[0152] 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.

[0153] 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.

[0154] [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.

[0155] [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 the sealing layers described in paragraphs

[0210] to

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

[0156] [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.

[0157] [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.

[0158] [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.

[0159] [Compounds] This invention also includes inventions of specific compounds.

[0160] 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.

[0161] [Compounds used in photoelectric conversion films] The following lists the materials used in the photoelectric conversion films.

[0162] [Synthesis of Compound C-12] Compound C-12 was synthesized according to the following scheme.

[0163]

[0164] In a round-bottom flask, aldehyde (compound F-1) (500 mg), malononitrile (83 g), and acetic anhydride (7.5 ml) were added and stirred at 110°C for 90 minutes. After heating, the reaction mixture was added dropwise to MeOH, and the precipitated solid was filtered off. The crude solution was subjected to column chromatography (toluene / ethyl acetate) to remove the solvent. The obtained solid was recrystallized in dichloromethane / MeOH, the crystals were filtered, and the mixture was vacuum dried. The obtained crystals were purified by sublimation to obtain 239 mg of compound C-12 (yield 51%). １ The H-NMR (Nuclear Magnetic Resonance) data is shown below. １ H-NMR (CDCl ３ ): δ=7.92 (2H, d), 7.52 (2H, m), 7.38 (4H, m), 6.64(1H, d), 6.11 (2H, m), 4.92 (1H, d), 2.19 (12H, d)

[0165] The compounds used in each example and comparative example for photoelectric conversion films other than compound C-12 are synthesized in accordance with the synthesis method for compound C-12.

[0166] [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-18 are specific compounds, and compounds D-1 to D-7 are comparative compounds.

[0167]

[0168]

[0169] [n-type organic semiconductor] ・C60: Fullerene (C ６０ )

[0170] [p-type organic semiconductor]

[0171]

[0172] [Evaluation] The quantum efficiency of the photoelectric conversion element when receiving green-red light (wavelength 600 nm), the dependence of the quantum efficiency on the electric field strength, the response speed, and the manufacturability were evaluated using the following methods.

[0173] [Fabrication of Photoelectric Conversion Element] A photoelectric conversion element in the form shown in Figure 2 was 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 was deposited on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and then a compound (EB-1) was 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)) were deposited on the electron blocking film 16A. ６０ A p-type organic semiconductor (compound E-1) and a photoelectron ion (ITO) were co-deposited by vacuum deposition to form a film with a single-layer thickness of 80 nm for each. This formed a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. The deposition rate of the photoelectric conversion film 12 was set to 1.0 Å / sec. Furthermore, compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming an SiO film as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al) was deposited thereon by ALCVD (Atomic Layer Chemical Vapor Deposition). ２ O ３ A layer was formed, and the resulting laminate was heated in a glove box at 150°C for 30 minutes to obtain a photoelectric conversion element.

[0174]

[0175] [Dark Current] The dark current of each obtained photoelectric conversion element was measured using the following method. 2.5 × 10⁻¹⁰ ions were applied to the lower and upper electrodes of each photoelectric conversion element. ５ A voltage was applied to achieve an electric field strength of V / cm, and the current value in the dark (dark current) was measured. As a result, the dark current for all photoelectric conversion elements was 50 nA / cm. ２ The following was observed, confirming that it exhibited a sufficiently low dark current.

[0176] [Quantum Efficiency] The quantum efficiency of each photoelectric conversion element was measured when it received blue-green light using the following method. 2.0 × 10⁻¹⁰ ５ After applying a voltage to achieve an electric field strength of V / cm, light was irradiated from the upper electrode (transparent conductive film) side, and the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 600 nm was evaluated. The photoelectric conversion efficiency of each photoelectric conversion element (= (photoelectric conversion efficiency of each photoelectric conversion element) / (photoelectric conversion efficiency of the photoelectric conversion element of Example 1-1)) was calculated with the photoelectric conversion efficiency of Example 1-1 set to 1, and the quantum efficiency was evaluated from the obtained value according to the evaluation criteria below. A quantum efficiency of B or higher is preferable.

[0177] A: 1.1 or higher B: 0.9 or higher but less than 1.1 C: Less than 0.9

[0178] [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 was evaluated using the following method. In the evaluation of [quantum efficiency] above, the voltage applied to each photoelectric conversion element was 7.5 × 10⁻⁶. ４ Except for changing the electric field strength to V / cm, the procedure was the same, resulting in 7.5 × 10 ４ The quantum efficiency at V / cm was measured. The electric field strength dependence of the quantum efficiency was calculated according to equation (S1), and the electric field strength dependence of the quantum efficiency was 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 600 nm for the photoelectric conversion element of Example 1-1 was 7.5 × 10⁻¹⁰. ４ Photoelectric conversion efficiency at V / cm and electric field strength of 2.0 × 10⁻¹⁰ at a wavelength of 600 nm for the photoelectric conversion element of Example 1-1. ５ This is compared with the photoelectric conversion efficiency at V / cm. For the dependence of quantum efficiency on electric field strength, an evaluation of C or higher is preferable. Equation (S1): Electric field strength dependence of quantum efficiency = (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 × 10⁻⁶) ５ Photoelectric conversion efficiency in V / cm)

[0179] A: The electric field strength dependence of the quantum efficiency is 0.9 or more B: The electric field strength dependence of the quantum efficiency is 0.8 or more and less than 0.9 C: The electric field strength dependence of the quantum efficiency is 0.7 or more and less than 0.8 D: The electric field strength dependence of the quantum efficiency is less than 0.7

[0180] 〔Response speed〕 For each photoelectric conversion element, the response speed when receiving green-red light was evaluated by the following method. A voltage was applied to the photoelectric conversion element so that the electric field strength became 2.0 × 10 ５ V / cm. Then, an LED (light emitting diode) was instantaneously lit to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 600 nm at that time was measured with an oscilloscope, and the rise time from 0% signal intensity to 97% signal intensity was measured. When the rise time of the photoelectric conversion elements of Examples 1-5 was set to 1, the rise time of each photoelectric conversion element (= (the rise time of each photoelectric conversion element) / (the rise time of the photoelectric conversion elements of Examples 1-5)) was obtained, and the response speed was evaluated according to the following evaluation criteria. A response speed of B or more is preferably evaluated.

[0181] A: Less than 0.9 B: 0.9 or more and less than 2.0 C: 2.0 or more

[0182] 〔Manufacturing suitability〕 For each photoelectric conversion element, the manufacturing suitability was evaluated by the following method. In the above 〔Fabrication of photoelectric conversion element〕, except that the film formation rate of the photoelectric conversion film 12 was set to 3.0 Å / sec, the photoelectric conversion elements (B) of each example or each comparative example were fabricated in the same procedure. For the obtained photoelectric conversion element (B), the photoelectric conversion efficiency of the photoelectric conversion element (B) was measured in the same manner as in the above 〔Quantum efficiency〕. The photoelectric conversion element in which the film formation rate of the photoelectric conversion film 12 obtained in the above 〔Fabrication of photoelectric conversion element〕 was 1.0 Å / sec was defined as the photoelectric conversion element (A), and the relative ratio B / A (= the photoelectric conversion efficiency of the photoelectric conversion element (B) / the photoelectric conversion efficiency of the photoelectric conversion element (A)) of the quantum efficiency was calculated. From the obtained value, the manufacturing suitability was evaluated according to the following evaluation criteria. The closer the value of the relative ratio B / A is to 1, the less likely the performance of the photoelectric conversion element is to deteriorate even when the film formation rate is increased, that is, the manufacturing suitability is excellent. A manufacturing suitability of B or more is preferably evaluated.

[0183] A: The relative ratio B / A is 0.90 or more. B: The relative ratio B / A is 0.85 or more and less than 0.90. C: The relative ratio B / A is less than 0.85.

[0184] [Results]

[0185] The evaluation results are shown in Table 1 below. In the table, in the column of "Formula (1)", when the photoelectric conversion film contains the compound represented by Formula (1), it is designated as "A", and in other cases, it is designated as "B". In the table, in the column of "Formula (2)", when the compound represented by Formula (1) is the compound represented by Formula (2), it is designated as "A", and in other cases, it is designated as "B". In the table, in the column of "X ２１ , X ２４ = N", when X ２１ and X ２４ are nitrogen atoms in Formula (2), it is designated as "A", and in other cases, it is designated as "B". In the table, in the column of "R ５ , R ６ = (B - 1)", when at least one of R ５ and R ６ is the group represented by Formula (B - 1) in Formula (2), it is designated as "A", and in other cases, it is designated as "B". In the table, in the column of "Formula (3)", when the compound represented by Formula (1) is the compound represented by Formula (3), it is designated as "A", and in other cases, it is designated as "B". In the table, in the column of "R ８ ≠ R ７ ", when R ８ and R ７ are different groups from each other in Formula (3), it is designated as "A", and in other cases, it is designated as "B". In the table, in the column of "(A - 3)(A - 4)", when A in Formula (1) is the group represented by Formula (A - 3) or the group represented by Formula (A - 4), it is designated as "A", and in other cases, it is designated as "B". In the table, in the column of "(A - 5)(A - 6)(A - 7)", when A in Formula (1) is the group represented by Formula (A - 5), Formula (A - 6), or Formula (A - 7), it is designated as "A", and in other cases, it is designated as "B".

[0186]

[0187] As shown in Table 1, the photoelectric conversion element of the present invention was confirmed to have low dependence of the field strength on the quantum efficiency when receiving green-red light. Furthermore, the photoelectric conversion element of the present invention was confirmed to have excellent quantum efficiency and response speed when receiving green-red light, as well as excellent manufacturability.

[0188] From a comparison of Examples 1-4 with other examples, it was confirmed that when the specific compound is the compound represented by formula (2) or formula (3), the quantum efficiency and response speed are superior. From a comparison of Examples 1-1, 1-3, 1-5, 1-7, 1-9, and 1-11 with other examples, it was confirmed that when the specific compound is the compound represented by formula (2), the electric field strength dependence of the quantum efficiency is superior. From a comparison of Example 1-8 with other examples, it was confirmed that in formula (2), X ２１ and X ２４ When R is a nitrogen atom, it was confirmed that the dependence of quantum efficiency on the electric field strength, quantum efficiency, and response speed are superior. From a comparison of Examples 1-13 with other examples, in formula (2), R ５ and R ６ It was confirmed that the electric field strength dependence of the quantum efficiency is better when at least one of the groups is represented by formula (B-1). From a comparison of Examples 1-1, 1-3, and 1-7 with other examples, R ８ and R ７ It was confirmed that when the groups are different from each other, the quantum efficiency and response speed are superior. From a comparison of Examples 1-2, 1-8, and 1-13, it was confirmed that when A is a group represented by formula (A-5), formula (A-6), or formula (A-7), the manufacturability is superior.

[0189] 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film

Claims

1. A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1). In formula (1), R １ , R ２ , R ３ , R ４ , and R ５ each independently represents a hydrogen atom or a substituent. X represents -NR Ｘ１ - or -C(R Ｘ２ )(R Ｘ３ )-. R Ｘ１ represents a hydrogen atom or a substituent. R Ｘ２ and R Ｘ３ each independently represents a substituent. However, when X represents -C(R Ｘ２ )(R Ｘ３ )-, at least one of R Ｘ２ and R Ｘ３ represents a substituent having 2 or more carbon atoms, or R Ｘ２ and R Ｘ３ may be bonded to each other to form a ring which may have a substituent. B represents an aromatic ring which may have a substituent. However, when X represents -NR Ｘ１ -, B represents an aromatic heterocyclic ring which may have a substituent. A represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (A-1), C contains 2 or more carbon atoms and represents a ring which may have a substituent. Y ａ１１ represents an oxygen atom, a sulfur atom, =NR ａ１１ , or =CR ａ１２ R ａ１３ . R ａ１１ represents a hydrogen atom or a substituent. R ａ１２ and R ａ１３ each independently represents a cyano group, -SO ２ R ａ１４ , -COOR ａ１５ , or -COR ａ１６ . R ａ１４ , R ａ１５ , and R ａ１６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Y ａ１２ is -O-, -NR ａ１７ -, -N=, -C(R ａ１８ ) (Caution ａ１９ )-,-CR ａ２０ = or -C (=Y ａ１３ ) represents R ａ１７ , R ａ１８ , R ａ１９ , and R ａ２０ Each of these independently represents a hydrogen atom or a substituent. ａ１３ is an oxygen atom, a sulfur atom, =NR ａ２７ , or =CR ａ２８ R ａ２９ Represents R ａ２７ , R ａ２８ , and R ａ２９ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position. In formula (A-2), R ａ２１ and R ａ２２ These are, independently, a cyano group and a -COOR group. ａ２３ , -COR ａ２４ , -CSOR ａ２５ , or -CSR ａ２６ Represents R ａ２３ , R ａ２４ , R ａ２５ , and R ａ２６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. However, the compound represented by formula (1) does not contain any carboxylic acid group and its salts, sulfonic acid group and its salts, or hydroxamic acid group and its salts.

2. The photoelectric conversion element according to claim 1, wherein the compound represented by formula (1) is the compound represented by formula (2). In formula (2), R １ , R ２ , R ３ , R ４ , R ５ , and A are, respectively, R in formula (1) above. １ , R ２ , R ３ , R ４ , R ５ , and is synonymous with A. R ６ X represents a hydrogen atom or substituent. ２１ , X ２２ , X ２３ , and X ２４ Each of these is independently -CR ２１ = or represents a nitrogen atom. However, X ２１ , X ２２ , X ２３ , and X ２４ At least one of them represents a nitrogen atom. ２１ X represents a hydrogen atom or substituent. ２１ , X ２２ , X ２３ , and X ２４ Two of the adjacent ones are -CR ２１ When representing =, the two adjacent -CR ２１ = R inside ２１ These groups may be bonded to each other to form a ring which may have substituents. However, the compound represented by formula (2) does not contain any carboxylic acid group and its salt, sulfonic acid group and its salt, or hydroxamic acid group and its salt.

3. X ２１ and X ２４ The photoelectric conversion element according to claim 2, wherein is a nitrogen atom.

4. R ５ and R ６ The photoelectric conversion element according to claim 2, wherein at least one of them is a group represented by formula (B-1). In formula (B-1), D represents a ring containing 2 or more carbon atoms and may have a substituent. R ｂ１１ represents a halogen atom, a silyl group, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or an alkoxy group which may have a substituent.

5. The photoelectric conversion element according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the formula (3). In the formula (3), R １ , R ２ , R ３ , R ４ , R ５ , and A are respectively the same as R １ , R ２ , R ３ , R ４ , R ５ , and A in the formula (1). R ７ and R ８ represent substituents. However, at least one of R ７ and R ８ represents a substituent having 2 or more carbon atoms, or R ７ and R ８ may combine with each other to form a ring which may have a substituent. X ３１ , X ３２ , X ３３ , and X ３４ each independently represent -CR ３１ = or a nitrogen atom. R ３１ represents a hydrogen atom or a substituent. When two adjacent ones of X ３１ , X ３２ , X ３３ , and X ３４ represent -CR <00�0119>=, the Rs in the two adjacent -CR ３１ = may combine with each other to form a ring which may have a substituent. However, the compound represented by the formula (3) does not contain any of a carboxylic acid group and its salt, a sulfonic acid group and its salt, and a hydroxamic acid group and its salt.​​ 6. R ７ and R ８ The photoelectric conversion element according to claim 5, wherein the groups are different from each other.

7. A photoelectric conversion element according to any one of claims 1 to 6, wherein A is a group represented by formula (A-3) or a group represented by formula (A-4). In formula (A-3), Y ａ３１ and Y ａ３２ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ３１ , or =CR ａ３２ R ａ３３ Represents R ａ３１ R represents a hydrogen atom or substituent. ａ３２ and R ａ３３ These are, independently, a cyano group and -SO ２ R ａ３４ , -COOR ａ３５ , or -COR ａ３６ Represents R ａ３４ , R ａ３５ , and R ａ３６ Each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. E represents a ring containing three or more carbon atoms and which may be substituted. * represents a bond position. In formula (A-4), R ａ４１ is a cyano group, -COOR ａ４２ , -COR ａ４３ , -CSOR ａ４４ , or -CSR ａ４５ Represents R ａ４２ , R ａ４３ , R ａ４４ , and R ａ４５ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position.

8. The photoelectric conversion element according to any one of claims 1 to 6, wherein A is a group represented by formula (A-5), a group represented by formula (A-6), or a group represented by formula (A-7). In formula (A-5), Y ａ５１ , Y ａ５２ , and Y ａ５３ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ５１ , or =CR ａ５２ R ａ５３ Represents R ａ５１ R represents a hydrogen atom or substituent. ａ５２ and R ａ５３ These are, independently, a cyano group and -SO ２ R ａ５４ , -COOR ａ５５ , or -COR ａ５６ Represents R ａ５４ , R ａ５５ , and R ａ５６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ５１ and Z ａ５２ Each of these is independently -NR ａ５７ - or -C (R ａ５８ ) (Caution ａ５９ ) represents R ａ５７ , R ａ５８ , and R ａ５９ Each of these independently represents a hydrogen atom or a substituent. * indicates a bond position. In formula (A-6), Y ａ６１ and Y ａ６２ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ６１ , or =CR ａ６２ R ａ６３ Represents R ａ６１ R represents a hydrogen atom or substituent. ａ６２ and R ａ６３ These are, independently, a cyano group and -SO ２ R ａ６４ , -COOR ａ６５ , or -COR ａ６６ Represents R ａ６４ , R ａ６５ , and R ａ６６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. F represents an optionally substituted aromatic ring containing two or more carbon atoms. * represents a bond position. In formula (A-7), * represents a bond position.

9. The photoelectric conversion element according to any one of claims 1 to 6, 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 formula (1) and the n-type organic semiconductor are mixed.

10. The photoelectric element according to claim 9, wherein the n-type organic semiconductor comprises fullerenes selected from the group consisting of fullerenes and their derivatives.

11. The photoelectric conversion element according to any one of claims 1 to 6, wherein the photoelectric conversion film further comprises a p-type organic semiconductor.

12. The photoelectric conversion element according to any one of claims 1 to 6, wherein the photoelectric conversion film further comprises a dye.

13. A photoelectric conversion element according to any one of claims 1 to 6, 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.

14. An image sensor having a photoelectric conversion element according to any one of claims 1 to 6.

15. A light sensor having a photoelectric conversion element according to any one of claims 1 to 6.

16. A method for manufacturing an image sensor, comprising a step of manufacturing a photoelectric conversion element according to any one of claims 1 to 6.

17. A compound represented by formula (1). In formula (1), R １ , R ２ , R ３ , R ４ , and R ５ Each of these independently represents a hydrogen atom or a substituent. X is -NR Ｘ１ - or -C (R Ｘ２ ) (Caution Ｘ３ ) represents R Ｘ１ R represents a hydrogen atom or substituent. Ｘ２ and R Ｘ３ Each of these independently represents a substituent. However, if X is -C(R) Ｘ２ ) (Caution Ｘ３ ) - When representing R Ｘ２ and R Ｘ３ At least one of them represents a substituent with 2 or more carbon atoms, or R Ｘ２ and R Ｘ３ These elements are bonded to each other to form a ring which may have substituents. B represents an aromatic ring which may have substituents. However, X is -NR Ｘ１ When represented by -, B represents an aromatic heterocycle which may have substituents. A represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (A-1), C represents a ring which contains two or more carbon atoms and may have substituents. Y ａ１１ This consists of an oxygen atom, a sulfur atom, and =NR ａ１１ , or =CR ａ１２ R ａ１３ Represents R ａ１１ R represents a hydrogen atom or a substituent. ａ１２ and R ａ１３ These are, independently, a cyano group and -SO ２ R ａ１４ , -COOR ａ１５ , or -COR ａ１６ Represents R ａ１４ , R ａ１５ , and R ａ１６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ１２ is -O-, -NR ａ１７ -, -N=, -C(R ａ１８ ) (Caution ａ１９ )-,-CR ａ２０ = or -C (=Y ａ１３ ) represents R ａ１７ , R ａ１８ , R ａ１９ , and R ａ２０ Each of these independently represents a hydrogen atom or a substituent. ａ１３ is an oxygen atom, a sulfur atom, =NR ａ２７ , or =CR ａ２８ R ａ２９ Represents R ａ２７ , R ａ２８ , and R ａ２９ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position. In formula (A-2), R ａ２１ and R ａ２２ These are, independently, a cyano group and a -COOR group. ａ２３ , -COR ａ２４ , -CSOR ａ２５ , or -CSR ａ２６ Represents R ａ２３ , R ａ２４ , R ａ２５ , and R ａ２６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. However, the compound represented by formula (1) does not contain any carboxylic acid group and its salts, sulfonic acid group and its salts, or hydroxamic acid group and its salts.

18. The compound according to claim 17, which is a compound represented by formula (2). In formula (2), R １ , R ２ , R ３ , R ４ , R ５ , and A are, respectively, R in formula (1) above. １ , R ２ , R ３ , R ４ , R ５ , and is synonymous with A. R ６ X represents a hydrogen atom or substituent. ２１ , X ２２ , X ２３ , and X ２４ Each of these is independently -CR ２１ = or represents a nitrogen atom. However, X ２１ , X ２２ , X ２３ , and X ２４ At least one of them represents a nitrogen atom. ２１ X represents a hydrogen atom or substituent. ２１ , X ２２ , X ２３ , and X ２４ Two of the adjacent ones are -CR ２１ When representing =, the two adjacent -CR ２１ = R inside ２１ These groups may be bonded to each other to form a ring which may have substituents. However, the compound represented by formula (2) does not contain any carboxylic acid group and its salt, sulfonic acid group and its salt, or hydroxamic acid group and its salt.

19. X ２１ and X ２４ The compound according to claim 18, wherein is a nitrogen atom.

20. R ５ and R ６ The compound according to claim 18, wherein at least one of the members is a group represented by formula (B-1). In formula (B-1), D represents a ring containing two or more carbon atoms, which may have substituents. ｂ１１ This represents a halogen atom, a silyl group, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted alkoxy group.

21. The compound according to claim 17, which is a compound represented by formula (3). In formula (3), R １ , R ２ , R ３ , R ４ , R ５ , and A are, respectively, R in formula (1) above. １ , R ２ , R ３ , R ４ , R ５ , and is synonymous with A. R ７ and R ８ represents a substituent. However, R ７ and R ８ At least one of them represents a substituent with 2 or more carbon atoms, or R ７ and R ８ These elements bond to each other to form a ring which may have substituents. ３１ , X ３２ , X ３３ , and X ３４ Each of these is independently -CR ３１ = or represents a nitrogen atom. R ３１ X represents a hydrogen atom or substituent. ３１ , X ３２ , X ３３ , and X ３４ Two of the adjacent ones are -CR ３１ When representing =, the two adjacent -CR ３１ = R inside ３１ These groups may bond to each other to form a ring which may have substituents. However, the compound represented by formula (3) does not contain any carboxylic acid group and its salt, sulfonic acid group and its salt, or hydroxamic acid group and its salt.

22. R ７ and R ８ The compound according to claim 21, wherein the groups are different from each other.

23. The compound according to any one of claims 17 to 22, wherein A is a group represented by formula (A-3) or a group represented by formula (A-4). In formula (A-3), Y ａ３１ and Y ａ３２ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ３１ , or =CR ａ３２ R ａ３３ Represents R ａ３１ R represents a hydrogen atom or substituent. ａ３２ and R ａ３３ These are, independently, a cyano group and -SO ２ R ａ３４ , -COOR ａ３５ , or -COR ａ３６ Represents R ａ３４ , R ａ３５ , and R ａ３６ Each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. E represents a ring containing three or more carbon atoms and which may be substituted. * represents a bond position. In formula (A-4), R ａ４１ is a cyano group, -COOR ａ４２ , -COR ａ４３ , -CSOR ａ４４ , or -CSR ａ４５ Represents R ａ４２ , R ａ４３ , R ａ４４ , and R ａ４５ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position.

24. The compound according to any one of claims 17 to 22, wherein A is a group represented by formula (A-5), a group represented by formula (A-6), or a group represented by formula (A-7). In formula (A-5), Y ａ５１ , Y ａ５２ , and Y ａ５３ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ５１ , or =CR ａ５２ R ａ５３ Represents R ａ５１ R represents a hydrogen atom or substituent. ａ５２ and R ａ５３ These are, independently, a cyano group and -SO ２ R ａ５４ , -COOR ａ５５ , or -COR ａ５６ Represents R ａ５４ , R ａ５５ , and R ａ５６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ａ５１ and Z ａ５２ Each of these is independently -NR ａ５７ - or -C (R ａ５８ ) (Caution ａ５９ ) represents R ａ５７ , R ａ５８ , and R ａ５９ Each of these independently represents a hydrogen atom or a substituent. * indicates a bond position. In formula (A-6), Y ａ６１ and Y ａ６２ These are, independently, an oxygen atom, a sulfur atom, and =NR ａ６１ , or =CR ａ６２ R ａ６３ Represents R ａ６１ R represents a hydrogen atom or substituent. ａ６２ and R ａ６３ These are, independently, a cyano group and -SO ２ R ａ６４ , -COOR ａ６５ , or -COR ａ６６ Represents R ａ６４ , R ａ６５ , and R ａ６６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. F represents an optionally substituted aromatic ring containing two or more carbon atoms. * represents a bond position. In formula (A-7), * represents a bond position.

Images