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

Abstract

The present invention provides a photoelectric conversion element in which the quantum efficiency with respect to blue light has low dependency on electric field intensity, and provides an imaging element, an imaging element production method, an optical sensor, and a compound. A photoelectric conversion element according to the present invention comprises an electroconductive film, a photoelectric conversion film, and a transparent electroconductive film in the stated order, the photoelectric conversion film containing a compound represented by formula (1).

Description

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

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

[0002] In recent years, development of elements having a photoelectric conversion film and organic electroluminescence (EL) elements has progressed as organic electronic devices. For example, Patent Document 1 discloses a photoelectric conversion element having a photoelectric conversion film with a narrow half-width of the absorption peak and excellent photoelectric conversion efficiency, the photoelectric conversion element containing a compound having a specific structure represented by formula (1).

[0003] International Publication No. 2019 / 189134

[0004] On the other hand, with the demand for improved performance of image sensors, optical sensors, and the like, there is a demand for photoelectric conversion elements that exhibit excellent characteristics. One of the characteristics required for a photoelectric conversion element is, for example, excellent electric field strength dependency of quantum efficiency for blue light. In response to this demand, the present inventors fabricated and investigated a photoelectric conversion element using the compound disclosed in Patent Document 1, and found that the electric field strength dependency of quantum efficiency for blue light needed to be improved. The blue light referred to above refers to light with a wavelength of 400 to 550 nm.

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

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

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described below. [2] B １ [3] The photoelectric conversion element according to [1], wherein R is a group represented by the above formula (B-1). ５ ~R ７[4] The photoelectric conversion element according to [1] or [2], wherein at least two of R represent hydrogen atoms. ３ and R ４ [5] The photoelectric conversion element according to any one of [1] to [3], wherein A is a group different from A. １ represents a group represented by formula (A-2) described later. [6] The photoelectric conversion element according to any one of [1] to [5], wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed by mixing a compound represented by formula (1) described later with the n-type organic semiconductor. [7] The photoelectric conversion element according to [6], wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof. [8] The photoelectric conversion element according to any one of [1] to [7], wherein the photoelectric conversion film further contains a p-type organic semiconductor. [9] The photoelectric conversion element according to any one of [1] to [8], wherein the photoelectric conversion film further contains a dye.

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

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

[10] .

[12] An optical sensor having the photoelectric conversion element according to any one of [1] to

[10] .

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

[10] .

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

[15] B １ is a group represented by the above formula (B-1). ５ ~R ７

[17] The compound according to

[14] or

[15] , wherein at least two of R represent a hydrogen atom. ３ and R ４

[18] The compound according to any one of

[14] to

[16] , wherein A １ represents a group represented by formula (A-2) described below.

[0008] According to the present invention, a photoelectric conversion element having a quantum efficiency for blue light that has little dependence on electric field strength can be provided. The present invention also provides an imaging element, a method for manufacturing an imaging element, an optical sensor, and a compound.

[0009] 1 is a schematic cross-sectional view showing an example of the configuration of a photoelectric conversion element.

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

[0011] The meaning of each description in this specification is as follows. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In this specification, a hydrogen atom may be a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom, etc.).

[0012] In this specification, with respect to compounds that may have geometric isomers (cis-trans isomers), the general formula or structural formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.

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

[0014] Unless otherwise specified, the bonding direction of a divalent group (e.g., -CO-O-) represented in this specification is not limited. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be either "X-O-CO-Z" or "X-CO-O-Z."

[0015] The symbol "*" shown in a chemical formula represents a bonding position unless otherwise specified. In this specification, when there are multiple substituents and linking groups, etc. (hereinafter also referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are specified at the same time, it means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc. In this specification, unless otherwise specified, "substituents" include groups exemplified as the substituent W described below.

[0016] (Substituent W) The substituent W in this specification will be described. Examples of the substituent W include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (a heteroaryl group, or an aliphatic heterocyclic group), a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryl ... Examples of the substituent W include an alkyloxy group, a primary, secondary, or tertiary amino group (including an anilino group), an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a carboxy group, a phosphate group, a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, and a boronic acid group. Furthermore, each of the above groups may further have a substituent (e.g., one or more of the above groups, etc.) if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. Furthermore, when the substituent W has a carbon atom, the number of carbon atoms contained in the substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30.

[0017] The compound of the present invention (compound represented by formula (1)) may have, as a substituent, a carboxy group and its salts, a phosphate group and its salts, a sulfonic acid group and its salts, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) ２ It is also preferred that the aryl group does not have a substituent selected from the group consisting of a primary amino group, a primary amino group, and a primary amino group.

[0018] In this specification, the aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, the phrase "the aliphatic hydrocarbon group may have an etheric oxygen atom" means that the aliphatic hydrocarbon group may have a divalent linking group represented by -O- in the middle or at the end. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups. Furthermore, unless otherwise specified in this specification, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and a cyclopentyl group. Furthermore, the alkyl group may be a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have these ring structures as partial structures. In the alkyl group that may have a substituent, examples of the substituent that the alkyl group may have include the groups exemplified for the substituent W. Of these, an aryl group (preferably having 6 to 18 carbon atoms, more preferably having 6 carbon atoms), a heteroaryl group (preferably having 5 to 18 carbon atoms, more preferably having 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom) is preferred.

[0019] In this specification, unless otherwise specified, the alkyl group moiety in the alkoxy group is preferably the above-mentioned alkyl group. The alkyl group moiety in the alkylthio group is preferably the above-mentioned alkyl group. In the alkoxy group which may have a substituent, examples of the substituent that the alkoxy group may have include the same as the substituent in the alkyl group which may have a substituent. In the alkylthio group which may have a substituent, examples of the substituent that the alkylthio group may have include the same as the substituent in the alkyl group which may have a substituent.

[0020] In this specification, unless otherwise specified, the alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20. In the alkenyl group which may have a substituent, examples of the substituent that the alkenyl group may have include the same as the substituents in the alkyl group which may have a substituent. In this specification, unless otherwise specified, the alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20. In the alkynyl group which may have a substituent, examples of the substituent that the alkynyl group may have include the same as the substituents in the alkyl group which may have a substituent.

[0021] In this specification, unless otherwise specified, an aromatic ring or an aromatic ring constituting an aromatic ring group may be either a monocyclic ring or a polycyclic ring (e.g., 2 to 6 rings, etc.). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure. A polycyclic (e.g., 2 to 6 rings, etc.) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6, etc.) condensed aromatic ring structures as a ring structure. The number of ring members in the aromatic ring is preferably 5 to 15. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. When the aromatic ring is an aromatic heterocyclic ring, the number of heteroatoms contained as ring member atoms is, for example, 1 to 10. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring.Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (e.g., a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (e.g., a 1,2,4,5-tetrazine ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a naphthopyrrole ring, a naphthofuran ring, a naphthothiophene ring, a naphthoimidazole ring, a naphthoxazole ring, a pyrroloimidazole ring (e.g., a 5H-pyrrolo[1,2-a]imidazole ring), an imidazooxazole ring (e.g., an imidazo[2,1-b]oxazole ring). , thienothiazole rings (for example, thieno[2,3-d]thiazole rings, etc.), benzothiadiazole rings, benzodithiophene rings (for example, benzo[1,2-b:4,5-b']dithiophene rings, etc.), thienothiophene rings (for example, thieno[3,2-b]thiophene rings, etc.), thiazolothiazole rings (for example, thiazolo[5,4-d]thiazole rings, etc.), naphthodithiophene rings (for example, naphtho[2,3 [2,1-b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc.), benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring, and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring.

[0022] As used herein, the term "aromatic ring group" includes, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic ring. As used herein, the term "aryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic hydrocarbon ring among the above-mentioned aromatic rings. As used herein, the term "heteroaryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic heterocycle among the above-mentioned aromatic rings. As used herein, the term "arylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above-mentioned aromatic rings. As used herein, the term "heteroarylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above-mentioned aromatic rings. In the optionally substituted aromatic ring, optionally substituted aromatic ring group, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted arylene group, and optionally substituted heteroarylene group, the types of substituents that these may have include, for example, the groups exemplified for the substituent W. When these groups which may have a substituent have a substituent, the number of the substituents may be one or more (for example, 1 to 4, etc.).

[0023] As used herein, the term "non-aromatic ring" refers to a ring structure that is not aromatic, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle. Examples of the aliphatic hydrocarbon ring include cycloalkanes, cycloalkenes, and cycloalkynes. As used herein, the term "aliphatic heterocyclic group" refers to, for example, a group obtained by removing one hydrogen atom from the aliphatic heterocycle. As used herein, the number of ring members in the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 6 to 8. Examples of heteroatoms contained in the aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred. Examples of the aliphatic heterocycle constituting the aliphatic heterocyclic group include a pyrrolidine ring, an oxolane ring (tetrahydrofuran ring), a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring (pentamethylene sulfide ring), a piperazine ring, a morpholine ring, a quinuclidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, and a γ-butyrolactone ring.

[0024] [Photoelectric conversion element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) described later (hereinafter also referred to as a "specific compound").

[0025] Although the reason why the photoelectric conversion element having the above configuration can solve the problem of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. For a photoelectric conversion element to solve the problem of the present invention and also satisfy other performance requirements, it is important that the dye contained in the photoelectric conversion film has strong absorption in the wavelength region corresponding to blue light, that the dyes do not aggregate excessively (the dyes are not too crystalline), and that the energy levels are appropriately positioned. Although the detailed mechanism is unknown, the inventors have solved the problem of the present invention by using a specific compound with a structure represented by formula (1) to create a dye that satisfies the above requirements. Hereinafter, a smaller electric field intensity dependence of the quantum efficiency for blue light is also referred to as a "better effect of the present invention."

[0026] FIG. 1 shows a cross-sectional schematic diagram of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in FIG. 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 functioning as an upper electrode are stacked in this order. FIG. 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in FIG. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be changed as appropriate depending on the application and characteristics.

[0027] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15. When the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 is applied between the pair of electrodes. －５ ~1 x 10 ７In terms of performance and power consumption, it is preferable to apply a voltage of 1×10 V / cm. －４ ~1 x 10 ７ V / cm is more preferable, and 1×10 －３ ~5 x 10 ６ V / cm is more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an imaging element, a voltage can be applied in a similar manner. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0028] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film.

[0029] <Specific Compound> The photoelectric conversion film contains a compound (specific compound) represented by formula (1).

[0030]

[0031] In formula (1), R １ and R ２ R each independently represents a hydrogen atom or a substituent. １ and R ２ Examples of the substituent represented by R include the groups exemplified above for the substituent W. １ and R ２ is preferably a hydrogen atom.

[0032] In formula (1), R ３ and R ４ R each independently represents an aliphatic hydrocarbon group which may have a substituent. Aliphatic hydrocarbon groups have a lower tendency to aggregate than aromatic ring structures, etc., and therefore can suppress the crystallinity of a specific compound, resulting in excellent device performance. ３ and R ４ may be the same group, but R ３ and R ４and are preferably different groups. Examples of the substituent that the aliphatic hydrocarbon group may have include the groups exemplified above for the substituent W. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear or branched is preferred in terms of suppressing the crystallinity of the specific compound. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The linear aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 3, and particularly preferably 1 to 2. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 4. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 6.

[0033] In formula (1), R ５ ~R ７ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified as the substituent W described above, and among these, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent is preferred, and an aliphatic hydrocarbon group which may have a substituent is more preferred. Examples of the substituent that the aliphatic hydrocarbon group, aromatic ring group, or aliphatic heterocyclic group may have include the substituents exemplified as the substituent W described above.

[0034] The aliphatic hydrocarbon group may be linear, branched, or cyclic, with linear or branched being preferred. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The linear aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 3, and particularly preferably 1 to 2. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 4. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 6.

[0035] The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic ring group may be either monocyclic or polycyclic. When the aromatic ring group has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 3. The number of ring members in the aromatic ring group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 to 8. The number of carbon atoms in the aromatic ring group is preferably 4 to 18, more preferably 4 to 10. The definition and specific examples of aromatic hydrocarbon groups are as described above, but examples include a phenyl group. Examples of heteroatoms contained in the aromatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. The definition and specific examples of aromatic heterocyclic groups are as described above, but examples include a thiophene ring group, a furan ring group, and a selenophene ring group.

[0036] The definition of the aliphatic heterocyclic group is as described above. The number of ring members in the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8. The number of carbon atoms in the aliphatic heterocyclic group is preferably 1 to 20. Examples of heteroatoms contained in the aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.

[0037] The effect of the present invention is more excellent. ５ ~R ７Preferably, at least two of the substituents represent hydrogen atoms. Furthermore, the substituents are preferably linear or branched aliphatic hydrocarbon groups, more preferably linear or branched alkyl groups. The preferred number of carbon atoms in the aliphatic hydrocarbon group is as described above.

[0038] In formula (1), B １ represents a group represented by any one of formulas (B-1) to (B-3). １ Among these, a group represented by formula (B-1) is preferred.

[0039]

[0040] In formula (1), B １ is represented by formula (B-1), formula (1) is represented by formula (1-1), and in formula (1), B １ is represented by formula (B-2), formula (1) is represented by formula (1-2), and in formula (1), B １ is expressed by formula (B-1), formula (1) is expressed by formula (1-3).

[0041]

[0042] In formula (B-1), R ｂ１１ ~R ｂ１４ each independently represents a hydrogen atom or a substituent. ｂ１１ ~R ｂ１４ At least two of R represent substituents. ｂ１１ ~R ｂ１４ When at least two of R are substituents, the crystallinity of the specific compound can be suppressed. ｂ１１ ~R ｂ１４ Among R, it is preferred that two or three are substituents and the rest are hydrogen atoms. ｂ１１ ~R ｂ１４ It is more preferable that two of R are substituents and the remaining are hydrogen atoms. ｂ１１ ~R ｂ１４ Among them, R ｂ１２ and R ｂ１４ are substituents and the remaining is a hydrogen atom, or ｂ１１ and R ｂ１３ It is more preferred that two of the above are substituents and the remaining is a hydrogen atom.

[0043] Examples of the substituent include the groups exemplified by the above-mentioned substituent W. More specifically, examples of the substituent include electron-withdrawing groups such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms), perfluoroalkyl groups, cyano groups, nitro groups, acyl groups, alkylsulfonyl groups, and arylsulfonyl groups, silyl groups, alkoxy groups, alkylthio groups, amino groups, aliphatic hydrocarbon groups which may have a substituent, aromatic ring groups which may have a substituent, or aliphatic heterocyclic groups which may have a substituent. Examples of the substituent that the aliphatic hydrocarbon group, aromatic ring group, or aliphatic heterocyclic group may have include the substituents exemplified by the above-mentioned substituent W. Specific examples and preferred embodiments of the aliphatic hydrocarbon group, aromatic ring group, or aliphatic heterocyclic group are R in formula (1). ５ ~R ７ Specific examples and preferred embodiments of the aliphatic hydrocarbon group, aromatic ring group, or aliphatic heterocyclic group are the same as those described above.

[0044] The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2. The number of carbon atoms in the acyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 10. The number of carbon atoms in the arylsulfonyl group is preferably 6 to 10. Examples of the silyl group include -Si(R Ｓｉ１ ) ３ Examples of the group include a group represented by the following formula: Ｓｉ１ represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Examples of the substituent which the aliphatic hydrocarbon group, aromatic ring group, and aliphatic heterocyclic group may have include the groups exemplified for the substituent W. Ｓｉ１ Among these, an aliphatic hydrocarbon group is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. The number of carbon atoms in the alkoxy group and alkylthio group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2. The amino group is preferably a tertiary amino group. The number of carbon atoms in the amino group is preferably 2 to 10, more preferably 2 to 6.

[0045] R ｂ１１ ~R ｂ１４ Among these, the substituent represented by any one of the following is preferably a halogen atom or an aliphatic hydrocarbon group which may have a substituent, more preferably a chlorine atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and even more preferably a chlorine atom or an aliphatic hydrocarbon group having 1 or 2 carbon atoms.

[0046] In formula (B-2), R ｂ２１ ~R ｂ２６ R each independently represents a hydrogen atom or a substituent. ｂ２１ ~R ｂ２６ It is preferred that one or more of R ｂ１１ ~R ｂ１４ It is more preferred that one or two of R are substituents and the remaining are hydrogen atoms. ｂ２１ ~R ｂ２６ Among them, R ｂ２６ is preferably a substituent. Specific examples and preferred embodiments of the substituent are R ｂ１１ ~R ｂ１４ Among these, the substituent is preferably a halogen atom or an aliphatic hydrocarbon group which may have a substituent, more preferably a chlorine atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and even more preferably a chlorine atom or an aliphatic hydrocarbon group having 1 or 2 carbon atoms.

[0047] In formula (B-3), X ３１ ~X ３４ are each independently a nitrogen atom or —C(R ｂ３ ) = where X ３１ ~X ３４ At least one of X represents a nitrogen atom. ３１ ~X ３４ Among these, one or two are nitrogen atoms and the rest are -C(R ｂ３ )=, and X ３１ ~X ３４ One of them is a nitrogen atom and the rest are -C(R ｂ３ )=, and X ３１ ~X３４ Of these, X ３２ or X ３４ is a nitrogen atom, and the rest is -C(R ｂ３ It is more preferable that R ｂ３ represents a hydrogen atom or a substituent. ｂ３ Specific examples and preferred embodiments of the substituent represented by the formula (B-1) are ｂ１１ ~R ｂ１４ The specific examples and preferred embodiments are the same as those of the substituents represented by any one of the following: ｂ３ Among these, the substituent represented by is preferably a halogen atom or an aliphatic hydrocarbon group which may have a substituent, more preferably a chlorine atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and still more preferably a chlorine atom or an aliphatic hydrocarbon group having 1 or 2 carbon atoms.

[0048] In the above formula (1), A １ represents a group represented by formula (A-1).

[0049]

[0050] In formula (A-1), C １ represents a monocycle which may have a substituent and contains five or more ring-forming atoms, of which four or more are carbon atoms. The ring-forming atoms are so-called ring member atoms. １ The atoms (four or more carbon atoms) forming five or more rings contained in formula (A-1) include the three carbon atoms specified in formula (A-1). The monocycle may be either an aromatic ring or a non-aromatic ring. The monocycle contains atoms forming five or more rings, and the number of atoms forming the ring is preferably 5 to 10, more preferably 5 or 6. Of the atoms forming the monocycle, the number of carbon atoms is preferably 4 to 10, more preferably 4 to 6.

[0051] The monocyclic ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a nitrogen atom, a sulfur atom, or an oxygen atom is preferred. The number of heteroatoms contained in the monocyclic ring is preferably 0 to 10, and more preferably 0 to 5. Of the carbon atoms forming the monocyclic ring, carbon atoms other than the three carbon atoms specified in formula (A-1) may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0052] C １ Examples of the substituent that may be possessed by include the groups exemplified for the substituent W above, and preferred are a halogen atom (preferably a chlorine atom), an alkyl group (which may be linear, branched, or cyclic and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a silyl group (for example, an alkylsilyl group. The alkyl group in the alkylsilyl group may be linear, branched, or cyclic and preferably has 1 to 4 carbon atoms, more preferably 1), or an aromatic ring group.

[0053] C １The monocyclic ring represented by the formula (I) which may have a substituent is preferably a ring used as an acidic nucleus (for example, the acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione, cincarpic acid, and 4,5-dimethyl-4-cyclopentene-1,3-dione; (b) 2,4,6-trioxohexahydropyrimidine nucleus: for example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof; Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl; 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl, and 1,3-dibutyl; 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl), and 1,3-di(p-ethoxycarbonylphenyl); 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl; and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl).

[0054] In the above formula (A-1), Z １ and Z ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｙ１ , or =C(R Ｙ２ ) (R Ｙ３ ) is represented. In terms of the effects of the present invention being more excellent, Z １ and Z ２ is preferably an oxygen atom or a sulfur atom. Ｙ１ represents a hydrogen atom, 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. Ｙ１ Examples of the substituent that may be possessed by each group represented by the formula (1) include the substituents exemplified above for the substituent W. Specific examples and preferred embodiments of the aliphatic hydrocarbon group, aromatic ring group, or aliphatic heterocyclic group are those represented by the formula (1) ５ ~R ７ Specific examples and preferred embodiments of the aliphatic hydrocarbon group, aromatic ring group, or aliphatic heterocyclic group are the same as those described above.

[0055] R Ｙ２ and R Ｙ３each independently represents a cyano group, —COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ Represents R Ｙ４ ~R Ｙ６ R each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Ｙ４ ~R Ｙ６ Examples of the substituent that each group represented by the formula (I) may have include the substituents exemplified above for the substituent W. The aliphatic hydrocarbon group is defined as above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The aromatic ring group is defined as above, and an aromatic hydrocarbon group is preferred, with a phenyl group being more preferred. The aliphatic heterocyclic group is defined as above, and the heteroatom that the aliphatic heterocyclic group has is preferably an oxygen atom, a sulfur atom, or a nitrogen atom.

[0056] A １ preferably represents a group represented by formula (A-2).

[0057]

[0058] In formula (A-2), Z １ ~Z ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｚ１ or = C(R Ｚ２ ) (R Ｚ３ ) is represented. In terms of the effects of the present invention being more excellent, Z １ ~Z ３ is preferably an oxygen atom or a sulfur atom. Ｚ１ represents a hydrogen atom, 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. Ｚ１ Preferred embodiments of each group represented by R Ｙ１ The preferred embodiments are the same as those of each group represented by the following formula:

[0059] R Ｚ２ and R Ｚ３ each independently represents a cyano group, —SO ２ R Ｚ４ , -COORＺ５ , or -COR Ｚ６ Represents R Ｚ４ ~R Ｚ６ R each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Ｚ４ ~R Ｚ６ A preferred embodiment of is R Ｙ４ ~R Ｙ６ This is the same as the preferred embodiment of

[0060] In the above formula (A-2), Y １ and Y ２ are each independently -N(R ｃ１ ) - or -C(R ｃ２ ) (R ｃ３ )-. ｃ１ ~R ｃ３ R each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. ｃ１ ~R ｃ３ Examples of the substituent that may be possessed by each group represented by the formula (I) include the substituents exemplified above for the substituent W. ｃ１ ~R ｃ３ Among these, an alkyl group or an aryl group is preferred, and an alkyl group is more preferred. The alkyl group may be linear, branched, or cyclic, and a linear group is preferred. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The aryl group may be monocyclic or polycyclic, and a phenyl group is preferred. The aryl group may further have a substituent, and examples of the substituent include the groups exemplified for the substituent W above.

[0061] Specific examples of the specific compound are shown below, but the present invention is not limited to these.

[0062]

[0063]

[0064]

[0065]

[0066] In the specific compounds exemplified above, * represents any of the following groups.

[0067]

[0068] The molecular weight of the specific compound is preferably 400 to 1200, more preferably 400 to 1000, and even more preferably 400 to 800. When the molecular weight is within the above range, the sublimation temperature of the specific compound is lowered, and it is presumed that the specific compound has excellent suitability for production.

[0069] The specific compound preferably has an ionization potential of −5.0 to −6.0 eV in a single film from the viewpoints of stability when used as a p-type organic semiconductor and matching of the energy level with an n-type organic semiconductor.

[0070] The maximum absorption wavelength of the specific compound is preferably in the wavelength range of 400 to 550 nm, more preferably in the range of 400 to 500 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the specific compound is insoluble in chloroform, the maximum absorption wavelength of the specific compound is determined by evaporating the specific compound and measuring the value using the specific compound in a film state.

[0071] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, an optical sensor, or a photovoltaic cell. The specific compound often functions as a dye in the photoelectric conversion film. The specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.

[0072] The specific compound may be purified as necessary. Examples of methods for purifying the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, and purification using an adsorbent such as activated carbon and recrystallization purification.

[0073] The content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound in terms of a single layer / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 20 to 50% by volume. Only one type of specific compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.

[0074] <n-Type Organic Semiconductor> The photoelectric conversion film preferably further contains an n-type organic semiconductor in addition to the specific compound. The n-type organic semiconductor is a compound different from the specific compound. The n-type organic semiconductor is an acceptor organic semiconductor material (compound) and refers to an organic compound that has the property of easily accepting electrons. In other words, the n-type organic semiconductor refers to the organic compound that has a larger electron affinity when two organic compounds are used in contact with each other. In other words, any organic compound can be used as the acceptor organic semiconductor as long as it is an organic compound with electron-accepting properties. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); and 5- to 7-membered heterocyclic compounds having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole). polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic acid anhydride; 1,4,5,8-naphthalenetetracarboxylic acid diimide derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; 3,4,9,10-perylenetetracarboxylic acid dianhydride; 3,4,9,10-perylenetetracarboxylic acid diimide derivatives; and the compounds described in paragraphs

[0056] to

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

[0075] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred. For example, fullerene C ６０ , fullerene C ７０, fullerene C ７６ , fullerene C ７８ , fullerene C ８０ , fullerene C ８２ , fullerene C ８４ , fullerene C ９０ , fullerene C ９６ , fullerene C ２４０ , fullerene C ５４０ and mixed fullerenes. Examples of fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerenes. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. Preferred fullerene derivatives are the compounds described in JP-A-2007-123707.

[0076] The n-type organic semiconductor may be an organic dye. Examples of the organic dye include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0077] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0078] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or in the range of more than 400 nm and 600 nm or less.

[0079] The photoelectric conversion film preferably has a bulk heterostructure formed by mixing a specific compound and an n-type organic semiconductor. The bulk heterostructure is a layer in the photoelectric conversion film in which the specific compound and the n-type organic semiconductor are mixed and dispersed. The photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs

[0013] to

[0014] of JP 2005-303266 A.

[0080] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0081] When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (thickness of the n-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.

[0082] When the n-type organic semiconductor contains fullerenes, the content of the fullerenes relative to the total content of the n-type organic semiconductors (film thickness of fullerenes converted into a single layer / total film thickness of each n-type organic semiconductor converted into a single layer × 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. Fullerenes may be used singly or in combination of two or more types.

[0083] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor) x 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume. When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the p-type organic semiconductor) x 100) is preferably 15 to 75% by volume, more preferably 30 to 75% by volume. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and a p-type organic semiconductor that is included as desired. "Substantially" means that the total content of the specific compound, n-type organic semiconductor, and p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume.

[0084] <p-Type Organic Semiconductor> The photoelectric conversion film preferably further contains a p-type organic semiconductor in addition to the specific compound. The p-type organic semiconductor is a compound different from the specific compound. The p-type organic semiconductor is a donor organic semiconductor material (compound) and refers to an organic compound that has the property of easily donating electrons. In other words, the p-type organic semiconductor refers to the organic compound that has a smaller ionization potential when two organic compounds are used in contact with each other. The p-type organic semiconductor may be used alone or in combination of two or more types.

[0085] Examples of p-type organic semiconductors include triarylamine compounds (e.g., N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), compounds described in paragraphs

[0128] to

[0148] of JP-A No. 2011-228614, compounds described in paragraphs

[0052] to

[0063] of JP-A No. 2011-176259, compounds described in paragraphs

[0119] to

[0158] of JP-A No. 2011-225544, compounds, compounds described in paragraphs

[0044] to

[0051] of JP-A No. 2015-153910 and compounds described in paragraphs

[0086] to

[0090] of JP-A No. 2012-094660, etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzthiophene benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of JP 2018-014474 A, compounds described in paragraphs

[0043] to

[0045] of WO 2016 / 194630 A, compounds described in paragraphs

[0025] to

[0037] and

[0099] to

[0109] of WO 2017 / 159684 A, compounds described in paragraphs

[0029] to

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

[0015] to

[0025] of WO 2018 / 207722 A, compounds described in paragraph [004 5] to

[0053] , compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

[0036] of JP2019-080052A, compounds described in paragraphs

[0044] to

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

[0041] to

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

[0034] to

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

[0033] to

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

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

[0019] to

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

[0031] to

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

[0036] to

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

[0055] to

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

[0041] to

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

[0044] to

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

[0041] to

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

[0042] to

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

[0043] to

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

[0031] to

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

[0036] to

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

[0045] to

[0048] of JP2020-010024A, etc.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. As p-type organic semiconductors, in addition to the above-mentioned compounds, JP 2021-163968 A, JP 2022-027575 A, JP 2022-123944 A, JP 2022-122839 A, JP 2022-120323 A, JP 2022-120273 A, JP 2022-115832 A, JP 2022-108268 A, JP 2022-100258 A,Compounds described in JP-A Nos. 2022-181226 and 2023-005703 can also be used, and these compounds are incorporated herein by reference. Examples of p-type organic semiconductors include compounds with a lower ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductors are listed below.

[0086]

[0087]

[0088]

[0089]

[0090] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0091] When the photoelectric conversion film contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the photoelectric conversion film (thickness of the p-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.

[0092] The photoelectric conversion film containing the specific compound is a non-luminescent film and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode). A non-luminescent film means a film having a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less. The lower limit is often 0% or more.

[0093] <Dye> The photoelectric conversion film may further contain a dye in addition to the specific compound. The dye is a compound different from the specific compound. The dye is preferably an organic dye. Examples of the organic dye include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, Examples of the organic dye include acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes and metal complex dyes, imidazoquinoxaline dyes described in WO 2020 / 013246, WO 2022 / 168856, JP 2023-10305 A, and JP 2023-10299 A, acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and donor-acceptor-donor type dyes in which two donors are bonded to an acceptor. Among these, cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred as organic dyes, as they have a maximum absorption wavelength in the preferred range described below.

[0094] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably from 400 to 700 nm, and even more preferably from 400 to 650 nm.

[0095] The content of the dye in the photoelectric conversion film relative to the total content of the specific compound and the dye (=(film thickness of the dye in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the dye in terms of a single layer)×100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.

[0096] <Film formation method> Examples of the film formation method for the photoelectric conversion film include dry film formation methods. Examples of dry film formation methods include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and vacuum deposition methods are preferred. When forming the photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0097] The thickness of the photoelectric conversion film is preferably from 10 to 1,000 nm, more preferably from 50 to 800 nm, and even more preferably from 50 to 500 nm.

[0098] [Electrodes] The photoelectric conversion element preferably has electrodes. The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of conductive materials include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident through the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and nanocarbon materials such as carbon nanotubes and graphene. Of these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0099] Typically, when the conductive film is made thinner than a certain range, the resistance value often increases rapidly. In a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10,000 Ω / □, and there is a wide degree of freedom in the range of film thickness that can be reduced. Furthermore, the thinner the film thickness of the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher the light transmittance. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and enhances photoelectric conversion performance. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance that accompany a reduction in film thickness, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0100] Depending on the application, the lower electrode 11 may be made transparent or may be made non-transparent and reflect light. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, etc., tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and granphenes.

[0101] The method for forming the electrodes can be appropriately selected depending on the electrode material. Specific examples include wet methods such as printing and coating; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD. When the electrode material is ITO, examples include electron beam methods, sputtering, resistance heating deposition, chemical reaction methods (such as the sol-gel method), and coating of a dispersion of indium tin oxide.

[0102] [Charge-blocking film: electron-blocking film, hole-blocking film] The photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge-blocking film. When the photoelectric conversion element has this film, the properties (quantum efficiency, response speed, etc.) of the resulting photoelectric conversion element are more excellent. Examples of the charge-blocking film include an electron-blocking film and a hole-blocking film.

[0103] [Electron Blocking Film] The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Polymer materials can also be used as the electron blocking film. Examples of polymer materials include polymers of phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and the like, and derivatives thereof.

[0104] The electron blocking film may be composed of multiple films. The electron blocking film may be composed of an inorganic material. In general, inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency. Examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0105] [Hole-Blocking Film] The hole-blocking film is an acceptor organic semiconductor material (compound), and the n-type organic semiconductors described above can be used. The hole-blocking film may be composed of multiple films.

[0106] Examples of methods for producing a charge blocking film include dry film formation and wet film formation. Examples of dry film formation include vapor deposition and sputtering. Vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition such as vacuum deposition being preferred. Examples of wet film formation include inkjet printing, spray printing, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with the inkjet method being preferred in terms of high-precision patterning.

[0107] The thickness of each of the charge blocking films (electron blocking film and hole blocking film) is preferably from 3 to 200 nm, more preferably from 5 to 100 nm, and even more preferably from 5 to 30 nm.

[0108] [Substrate] The photoelectric conversion element may further include a substrate. Examples of the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate. The substrate is usually positioned such that a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked in this order on the substrate.

[0109] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. The performance of photoelectric conversion materials may be significantly degraded in the presence of degrading factors such as water molecules. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of a ceramic such as a dense metal oxide, metal nitride, or metal nitride oxide, or diamond-like carbon (DLC), which does not allow water molecules to penetrate. Examples of sealing layers include those described in paragraphs

[0210] to

[0215] of JP 2011-082508 A, the contents of which are incorporated herein by reference.

[0110] [Method for manufacturing photoelectric conversion element] Examples of methods for manufacturing photoelectric conversion elements include known manufacturing methods. Specifically, for example, methods for manufacturing photoelectric conversion elements include a step of forming a conductive film on a substrate, a step of forming a photoelectric conversion film, and a step of forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer) in addition to the above. The method for forming each layer is as described above.

[0111] [Imaging element] An example of an application of a photoelectric conversion element is an imaging element. An imaging element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal and outputting the electrical signal pixel by pixel from the imaging element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The manufacturing method of an imaging element is not particularly limited, but examples include a method including the step of manufacturing the photoelectric conversion element described above.

[0112] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, a photocell and an optical sensor, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged linearly or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.

[0113] [Compound] The present invention also includes the invention of a compound. The compound of the present invention is the above-mentioned specific compound.

[0114] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0115] [Compounds used in photoelectric conversion film] The materials used in the photoelectric conversion film are shown below.

[0116] [Synthesis of Compound (D-1)] Compound (D-1) was synthesized according to the following scheme.

[0117]

[0118] <Synthesis of Compound (D-1-1)> 2,4-Dichlorophenylhydrazine hydrochloride (10.0 g, 46.8 mmol), 3-methyl-2-pentanone (9.38 g, 93.7 mmol), and acetic acid (200 mL) were placed in a glass reaction vessel and stirred at 110°C for 4 hours. The resulting reaction solution was allowed to cool to room temperature, and the solvent was evaporated under reduced pressure. The resulting residue was dissolved in ethyl acetate and washed with water and saturated brine. The resulting organic phase was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent (volume ratio): hexane / ethyl acetate = 1 / 1) to obtain compound (D-1-1) (6.9 g, yield 61%).

[0119] <Synthesis of Compound (D-1-2)> Compound (D-1-1) (6.0 g, 35.1 mmol), methyl p-toluenesulfonate (9.5 g, 49.6 mmol), and acetonitrile (45 mL) were placed in a glass reaction vessel and stirred at 150°C for 2 hours using a microwave device. The resulting reaction solution was allowed to cool to room temperature and diluted with water (90 mL), and then 2 M aqueous sodium hydroxide solution was added to adjust the pH to 8, followed by extraction with ethyl acetate. The resulting organic phase was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent (volume ratio): hexane / ethyl acetate = 9 / 1) to obtain compound (D-1-2) (5.2 g, yield 82%).

[0120] <Synthesis of Compound (D-1-3)> Compound (D-1-2) (3.0 g, 11.7 mmol) was added to a glass reaction vessel containing (chloromethylene)dimethyliminium chloride (5.50 g, 35.1 mmol) and acetonitrile (60 mL) and stirred at room temperature for 30 minutes. The resulting reaction solution was added dropwise to a mixture of 1 mol / L aqueous sodium hydroxide solution (45 mL) and ice (45 g). The mixture was stirred for 1 hour and then extracted with ethyl acetate. The resulting organic phase was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent (volume ratio): dichloromethane / ethyl acetate = 8 / 2) to obtain compound (D-1-3) (1.70 g, yield 51%).

[0121] <Synthesis of Compound (D-1)> Compound (D-1-3) (1.0 g, 3.51 mmol), 1,3-dimethylbarbituric acid (0.71 g, 4.56 mmol), and acetic anhydride (20 mL) were placed in a glass reaction vessel and stirred at 110°C for 4 hours. The resulting reaction solution was allowed to cool to room temperature, and the resulting precipitate was filtered and washed with methanol. The resulting crude product was purified by silica gel chromatography (eluent (volume ratio): toluene / ethyl acetate = 80:20) and further purified by sublimation to obtain compound (D-1) (1.1 g, yield 72%). The obtained compound (D-1) was identified by NMR (Nuclear Magnetic Resonance). Compound (D-1): １ H-NMR (400MHz, CDCl ３ ): δ (ppm) = 8.68 (1H, d), 7.66 (1H, d), 7.29 (1H, d), 7.14 (1H, d), 3.89 (3H, s), 3.39 (3 H, s), 3.38 (3H, s), 2.32-2.43 (1H, m), 2.04-2.15 (1H, m), 1.70 (3H, s), 0.48 (3H, t).

[0122] The compounds used in the photoelectric conversion film of each of the Examples and Comparative Examples other than the compound (D-1) were synthesized according to the synthesis method of the compound (D-1).

[0123] The materials used in the preparation of the photoelectric conversion element are shown below. Compounds D-1 to D-40 correspond to specific compounds used in the examples, and compounds C-1 to C-5 correspond to comparative compounds used in the comparative examples.

[0124]

[0125]

[0126]

[0127] [n-type organic semiconductor] Fullerene (C ６０ )

[0128] [p-type organic semiconductor]

[0129]

[0130] [Dye] In Test Y described later, the dye shown below was used.

[0131]

[0132] [Evaluation: Test X] The quantum efficiency, response speed, and electric field intensity dependency of the quantum efficiency when the photoelectric conversion element received blue light (wavelength 450 nm) were evaluated by the following methods.

[0133] [Fabrication of Photoelectric Conversion Element] A photoelectric conversion element having the configuration shown in FIG. 2 was fabricated using the various components shown above. Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a film of the lower electrode 11 (thickness: 30 nm), and further a film of compound (EB-1) was formed on the lower electrode 11 by vacuum heating evaporation to form an electron blocking film 16A (thickness: 30 nm). Next, with the glass substrate at room temperature, each material shown in Table 1 (evaluation compound, p-type organic semiconductor, and n-type organic semiconductor (C ６０)) were co-deposited by vacuum deposition in a volume ratio of 1:1:1 in terms of a single layer, thereby forming a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. Compound (EB-2) was further deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After a SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al ２ O ３ The resulting laminate was heated in a glove box at 150° C. for 30 minutes to obtain a photoelectric conversion element.

[0134]

[0135] [Dark Current] The dark current of each of the obtained photoelectric conversion elements was measured by the following method. ５ A voltage was applied to the photoelectric conversion element so as to obtain an electric field strength of 50 nA / cm. The current value in a dark place (dark current) was measured. As a result, the dark current was 50 nA / cm for all the photoelectric conversion elements. ２ It was confirmed that the dark current was sufficiently low.

[0136] [Quantum Efficiency] The quantum efficiency of each photoelectric conversion element was measured when blue light was received by the following method. ５ After applying a voltage to achieve an electric field strength of 1000 V / cm, light was irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 450 nm, and the quantum efficiency (relative ratio) was calculated according to formula (S1). From the obtained value, the quantum efficiency was evaluated according to the following evaluation criteria. Formula (S1): Quantum efficiency (relative ratio) = (photoelectric conversion efficiency of each photoelectric conversion element) / (photoelectric conversion efficiency of the photoelectric conversion element in Example 1-1)

[0137] A: Quantum efficiency (relative ratio) is 0.95 or more. B: Quantum efficiency (relative ratio) is 0.80 or more and less than 0.95. C: Quantum efficiency (relative ratio) is 0.60 or more and less than 0.80. D: Quantum efficiency (relative ratio) is less than 0.60.

[0138] [Response Speed] The response speed of each photoelectric conversion element when receiving blue light was evaluated by the following method. ５ A voltage was applied so that the intensity was 1000 V / cm. Thereafter, the LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 450 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity, and the relative response speed was calculated according to formula (S2). From the obtained value, the response speed was evaluated according to the following evaluation criteria. Formula (S2): Relative response speed = (rise time of each photoelectric conversion element at a wavelength of 450 nm) / (rise time of the photoelectric conversion element of Example 1-1 at a wavelength of 450 nm)

[0139] A: Relative response speed is less than 1.1 B: Relative response speed is 1.1 or more and less than 1.5 C: Relative response speed is 1.5 or more and less than 2.0 D: Relative response speed is 2.0 or more

[0140] [Dependence of Quantum Efficiency on Electric Field Strength] The dependence of quantum efficiency on electric field strength was evaluated for each photoelectric conversion element by the following method. ４ The quantum efficiency at 7.0 V / cm was measured. The electric field strength dependency of the quantum efficiency was calculated according to formula (S3), and the electric field strength dependency of the quantum efficiency was evaluated according to the following evaluation criteria. In formula (S3), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. The electric field strength dependency of the quantum efficiency is preferably rated B or higher. Formula (S3): Electric field strength dependency of quantum efficiency = (electric field strength of each photoelectric conversion element 7.0 × 10 ４ (quantum efficiency at an electric field strength of 2.0×10 V / cm) / (quantum efficiency at an electric field strength of 2.0×10 V / cm of each photoelectric conversion element)

[0141] A: The electric field strength dependency of quantum efficiency is 0.9 or more. B: The electric field strength dependency of quantum efficiency is 0.8 or more and less than 0.9. C: The electric field strength dependency of quantum efficiency is 0.7 or more and less than 0.8. D: The electric field strength dependency of quantum efficiency is less than 0.7.

[0142] [Result: Rating X]

[0143] The evaluation results of Test X are shown in Table 1 below. In the table, the column "Formula (B-1)" indicates the B １ is a group represented by formula (B-1), it is represented as "A", and in other cases it is represented as "B". ５ , R ６ =H" column is R ５ ~R ７ When at least two of the groups represent hydrogen atoms, the group is designated as "A", and when they do not, the group is designated as "B". ３ ≠R ４ " column indicates the R ３ and R ４ In the table, the column "(A-2)" indicates the group A for a specific compound. １ represents a group represented by formula (A-2), it is designated as "A", and in other cases it is designated as "B".

[0144]

[0145] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention has a small dependence of quantum efficiency on electric field strength when receiving blue light. １ is a group represented by formula (B-1), it was confirmed that the response speed when blue light was received was superior. ５ ~R ７ It was confirmed that when at least two of R represent hydrogen atoms, the response speed when blue light is received is superior. ３ and R ４It was confirmed that when A is a group different from A, the quantum efficiency when blue light is received is superior. １ It was confirmed that when represents a group represented by formula (A-2), the quantum efficiency and the electric field strength dependency of the quantum efficiency are more excellent.

[0146] [Evaluation: Test Y] Subsequently, a photoelectric conversion element was prepared using a dye other than the specific compound in addition to the specific compound or the comparative compound, and the quantum efficiency, response speed, and electric field strength dependence of the quantum efficiency of the photoelectric conversion element at wavelengths of 450 nm and 600 nm were evaluated by the following methods.

[0147] [Fabrication of Photoelectric Conversion Device] Each material shown in Table 2 (evaluation compound, p-type organic semiconductor, n-type organic semiconductor (C ６０ ) and dye) were co-deposited by a vacuum deposition method in a ratio of compound (specific compound or comparative compound):dye:p-type organic semiconductor:n-type organic semiconductor=1:1:2:2 in terms of a single film, to form a film, thereby forming a photoelectric conversion film 12, and the other procedures were the same as in Test X, to prepare photoelectric conversion elements of each Example and Comparative Example.

[0148] [Dark Current] The dark current was measured in the same manner as in Test X. As a result, the dark current was 50 nA / cm in all the photoelectric conversion elements. ２ It was confirmed that the dark current was sufficiently low.

[0149] [Quantum Efficiency] The quantum efficiency of each of the obtained photoelectric conversion elements was measured by the following method. ５ After applying a voltage to achieve an electric field strength of 1000 V / cm, light was irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 450 nm or 600 nm, and the quantum efficiency (relative ratio) was calculated according to formula (S4). From the obtained values, the quantum efficiency was evaluated according to the following evaluation criteria. Formula (S4): Quantum efficiency (relative ratio) = (quantum efficiency of each photoelectric conversion element at a wavelength of 450 nm or 600 nm) / (quantum efficiency of Example 2-1 at a wavelength of 450 nm or 600 nm)

[0150] The evaluation criteria for quantum efficiency at wavelengths of 450 nm and 600 nm are as follows: A: Quantum efficiency (relative ratio) is 0.95 or more; B: Quantum efficiency (relative ratio) is 0.80 or more and less than 0.95; C: Quantum efficiency (relative ratio) is 0.60 or more and less than 0.80; D: Quantum efficiency (relative ratio) is less than 0.60.

[0151] [Response Speed] The response speed of each of the obtained photoelectric conversion elements was evaluated by the following method. ５ A voltage was applied to the photoelectric conversion element so that the intensity was 100 V / cm. Thereafter, the LED was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 450 nm or 600 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity, and the relative response speed was calculated according to formula (S5). From the obtained values, the response speed was evaluated according to the following evaluation criteria. Formula (S5): Relative response speed = (rise time of each photoelectric conversion element at a wavelength of 450 nm or 600 nm) / (rise time of the photoelectric conversion element of Example 2-1 at a wavelength of 450 nm or 600 nm)

[0152] The evaluation criteria for the response speed at wavelengths of 450 nm and 600 nm are as follows: A: Relative response speed less than 1.1 B: Relative response speed 1.1 or more and less than 1.5 C: Relative response speed 1.5 or more and less than 2.0 D: Relative response speed 2.0 or more

[0153] [Dependence of Quantum Efficiency on Electric Field Strength] For each photoelectric conversion element, the dependence of quantum efficiency at wavelengths of 450 nm and 600 nm on electric field strength was evaluated by the following method. ４The quantum efficiency at 7.0 V / cm was measured. The electric field strength dependency of the quantum efficiency was calculated according to formula (S6), and the electric field strength dependency of the quantum efficiency was evaluated according to the following evaluation criteria. In formula (S6), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. The electric field strength dependency of the quantum efficiency is preferably rated B or higher. Formula (S6): Electric field strength dependency of quantum efficiency = (electric field strength of each photoelectric conversion element 7.0 × 10 ４ (quantum efficiency at an electric field strength of 2.0×10 V / cm) / (quantum efficiency at an electric field strength of 2.0×10 V / cm of each photoelectric conversion element)

[0154] The evaluation criteria for the electric field strength dependence of quantum efficiency at wavelengths of 450 nm and 600 nm are as follows: A: Electric field strength dependence of quantum efficiency is 0.9 or more B: Electric field strength dependence of quantum efficiency is 0.8 or more but less than 0.9 C: Electric field strength dependence of quantum efficiency is 0.7 or more but less than 0.8 D: Electric field strength dependence of quantum efficiency is less than 0.7

[0155] Table 2 shows the evaluation results of Test Y. The symbols in Table 2 are as described above for the symbols in Table 1.

[0156]

[0157] 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 and R ２ each independently represents a hydrogen atom or a substituent. R ３ and R ４ each independently represents an aliphatic hydrocarbon group which may have a substituent. R ５ to R ７ each independently represents a hydrogen atom or a substituent. A １ represents a group represented by formula (A-1). B １ represents a group represented by any one of formula (B-1) to formula (B-3). In formula (A-1), C １ may have a substituent, contains atoms forming five or more rings, and four or more of the atoms forming the ring are carbon atoms, and represents a monocyclic ring. Z １ and Z ２ each independently represents an oxygen atom, a sulfur atom, =NR Ｙ１ or =C(R Ｙ２ )(R Ｙ３ ). R Ｙ１ represents a hydrogen atom, 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. R Ｙ２ and R Ｙ３ each independently represents a cyano group, -COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ . R Ｙ４ to R Ｙ６ 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. In formula (B-1), R ｂ１１ to R ｂ１４ each independently represents a hydrogen atom or a substituent. However, at least two of R ｂ１１ to R ｂ１４ represent substituents. In formula (B-2), R ｂ２１ to R ｂ２６ each independently represents a hydrogen atom or a substituent. In formula (B-3), X ３１ ~X ３４ each independently represents a nitrogen atom or -C(R ｂ３ ). However, at least one of X ３１ ~X ３４ represents a nitrogen atom. R ｂ３ represents a hydrogen atom or a substituent. * represents the bonding position.

2. B １ The photoelectric conversion element according to claim 1, wherein B is a group represented by the formula (B-1).

3. R ５ ~R ７ The photoelectric conversion element according to claim 1, wherein at least two of R to R represent hydrogen atoms.

4. R ３ and R ４ The photoelectric conversion element according to claim 1, wherein are different groups.

5. A １ The photoelectric conversion element according to claim 1, wherein A represents a group represented by formula (A-2). In formula (A-2), Z １ to Z ３ each independently represents an oxygen atom, a sulfur atom, =NR Ｚ１ or =C(R Ｚ２ )(R Ｚ３ ). R Ｚ１ represents a hydrogen atom, 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. R Ｚ２ and R Ｚ３ each independently represents a cyano group, -SO ２ R Ｚ４ -COOR Ｚ５ or -COR Ｚ６ . R Ｚ４ to R Ｚ６ 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 １ and Y ２ each independently represents -N(R ｃ１ )- or -C(R ｃ２ )(R ｃ３ ). R ｃ１ to R ｃ３ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. * represents the bonding position.

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

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

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

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

10. The photoelectric conversion element according to claim 1, having one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

11. An imaging device having the photoelectric conversion element according to any one of claims 1 to 10.

12. An optical sensor having the photoelectric conversion element according to any one of claims 1 to 10.

13. A method for manufacturing an imaging device, having a step of manufacturing the photoelectric conversion element according to any one of claims 1 to 10.

14. A compound represented by formula (1). In formula (1), R １ and R ２ each independently represent a hydrogen atom or a substituent. R ３ and R ４ each independently represent an aliphatic hydrocarbon group which may have a substituent. R ５ to R ７ each independently represent a hydrogen atom or a substituent. A １ represents a group represented by formula (A-1). B １ represents a group represented by any one of formula (B-1) to formula (B-3). In formula (A-1), C １ may have a substituent, contains atoms forming five or more rings, and four or more of the atoms forming the rings are carbon atoms, and represents a monocyclic ring. Z １ and Z ２ each independently represent an oxygen atom, a sulfur atom, =NR Ｙ１ , or =C(R Ｙ２ )(R Ｙ３ ). R Ｙ１ represents a hydrogen atom, 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. R Ｙ２ and R Ｙ３ each independently represent a cyano group, -COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ . R Ｙ４ to R Ｙ６ each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. In formula (B-1), R ｂ１１ to R ｂ１４ each independently represent a hydrogen atom or a substituent. However, at least two of R ｂ１１ to R ｂ１４ represent substituents. In formula (B-2), R ｂ２１ to R ｂ２６ each independently represent a hydrogen atom or a substituent. In formula (B-3), X ３１ to X ３４ Each independently represents a nitrogen atom or -C(R ｂ３ ). However, X ３１ to X ３４ at least one of represents a nitrogen atom. R ｂ３ represents a hydrogen atom or a substituent. * represents the bonding position.

15. B １ The compound according to claim 14, wherein B is a group represented by the formula (B-1).

16. R ５ ~R ７ The compound according to claim 14, wherein at least two of R 17. R ３ and R ４ are different groups, and the compound according to claim 14.

18. A １ is a compound according to any one of claims 14 to 17, which represents a group represented by formula (A-2). In formula (A-2), Z １ to Z ３ each independently represents an oxygen atom, a sulfur atom, =NR Ｚ１ or =C(R Ｚ２ )(R Ｚ３ ). R Ｚ１ represents a hydrogen atom, 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. R Ｚ２ and R Ｚ３ each independently represents a cyano group, -SO ２ R Ｚ４ , -COOR Ｚ５ , or -COR Ｚ６ . R Ｚ４ to R Ｚ６ 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 １ and Y ２ each independently represents -N(R ｃ１ )- or -C(R ｃ２ )(R ｃ３ ). R ｃ１ to R ｃ３ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. * represents the bonding position.

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