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

Abstract

Provided are: a photoelectric conversion element that has excellent response speed when red light is received and has small electric field intensity dependency of the response speed; and an imaging element, an optical sensor, an imaging element production method, and a compound, which are related to the photoelectric conversion element. This photoelectric conversion element has an electroconductive film, a photoelectric conversion film, and a transparent electroconductive film, in the stated order. The photoelectric conversion film contains a compound represented by formula (1).

Description

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

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

[0002] In recent years, development of devices (e.g., image sensors) having photoelectric conversion films has progressed. For example, Patent Document 1 discloses, as a photoelectric conversion material, a photoactive compound having an acceptor-donor-acceptor structure and excellent volatility or vaporizability.

[0003] International Publication No. 2022 / 098917

[0004] With the demand for improved performance of imaging devices, optical sensors, and the like, there is a demand for photoelectric conversion elements that exhibit excellent characteristics. Examples of the characteristics required of photoelectric conversion elements include an excellent response speed when receiving red light. Furthermore, the response speed of the photoelectric conversion element is also required to be resistant to a decrease in response speed even when the electric field strength is changed, i.e., the electric field strength dependency of the response speed is small. In response to such demands, the present inventors fabricated and investigated a photoelectric conversion element containing the photoactive compound disclosed in Patent Document 1, and found that the response speed when receiving red light and the electric field strength dependency of the response speed needed to be improved. The red light referred to above refers to light with a wavelength of 600 to 780 nm.

[0005] Therefore, an object of the present invention is to provide a photoelectric conversion element that has an excellent response speed when receiving red light and that has a small dependency of the response speed on electric field strength. Another object of the present invention is to provide an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound related to the photoelectric conversion element.

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

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described below. [2] R ｂ１ and R ｂ２at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ７ and R ｂ８ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; Ｎ１ [3] The photoelectric conversion element according to [1], wherein R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. ｂ１ and R ｂ２ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ７ and R ｂ８ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; Ｎ１ [4] The photoelectric conversion element according to [1] or [2], wherein X represents an aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a substituent, or an aromatic ring group having 6 to 10 carbon atoms which has a substituent. ３ and X ４ are each independently -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１ [5] The photoelectric conversion element according to any one of [1] to [3], wherein in the formula (1), X represents -. ３ and X ４ are each independently -C(Rｂ１ R ｂ２ ) - or -NR Ｎ１ [6] The photoelectric conversion element according to any one of [1] to [4], wherein in the formula (1), X represents -. １ and X ２ are each independently -CR ａ１ [7] The photoelectric conversion element according to any one of [1] to [5], wherein in formula (C-1) described later, R ｃ１ and R ｃ２ At least one of R independently represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and in formula (C-2) described below, ｃ３ and R ｃ４

[0013] The photoelectric conversion element according to any one of [1] to [6], wherein at least one of the following represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms, which may have a substituent. [8] The photoelectric conversion element according to any one of [1] to [7], wherein the compound represented by formula (1) satisfies at least one of requirement 1 and requirement 2 described below. [9] The photoelectric conversion element according to [8], wherein the compound represented by formula (1) satisfies requirement 1.

[10] The photoelectric conversion element according to any one of [1] to [9], wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) described below with the n-type organic semiconductor.

[11] The photoelectric conversion element according to

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

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

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

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

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

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

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

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

[14] .

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

[14] .

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

[14] .

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

[19] R ｂ１ and R ｂ２ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ７ and Rｂ８ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; Ｎ１

[20] The compound according to

[18] , wherein R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. ｂ１ and R ｂ２ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ７ and R ｂ８ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; Ｎ１

[21] The compound according to

[18] or

[19] , wherein X represents an aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a substituent, or an aromatic ring group having 6 to 10 carbon atoms which has a substituent. ３ and X ４ are each independently -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１

[22] The compound according to any one of

[18] to

[20] , wherein in the above formula (1), X represents -. ３ and X ４ are each independently -C(R ｂ１ R ｂ２ ) - or -NR Ｎ１

[23] The compound according to any one of

[18] to

[21] , wherein X represents -. １ and X ２ are each independently -CR ａ１

[24] The compound according to any one of

[18] to

[22] , wherein R ｃ１ and R ｃ２At least one of R independently represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and in formula (C-2) described below, ｃ３ and R ｃ４

[25] The compound according to any one of

[18] to

[24] , wherein the compound represented by formula (1) satisfies at least one of requirement 1 and requirement 2 described below.

[26] The compound according to

[25] , wherein the compound represented by formula (1) satisfies requirement 1 described above.

[0008] According to the present invention, a photoelectric conversion element having an excellent response speed when receiving red light and a small dependency of the response speed on electric field strength can be provided. Furthermore, according to the present invention, an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound related to the photoelectric conversion element can also be provided.

[0009] 1 is a schematic cross-sectional view 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] 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."

[0014] 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.

[0015] (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. The specific compounds described below may have, as substituents, a carboxy group, a salt of a carboxy group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) ２ ) and / or has no primary amino groups.

[0016] In this specification, the aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Furthermore, in this specification, unless otherwise specified, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. 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.

[0017] 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.

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

[0019] In this specification, unless otherwise specified, an aromatic ring or an aromatic ring constituting an aromatic ring group may be either a monocyclic ring or a polycyclic ring (e.g., 2 to 6 rings, 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.

[0020] 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.).

[0021] 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.

[0022] [Photoelectric conversion element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) (hereinafter also referred to as a "specific compound").

[0023] Although the reason why a photoelectric conversion element having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The specific compound is a so-called ADA-type dye compound having a donor moiety (D) and an acceptor moiety (A). ADA-type dye compounds tend to have high aggregation properties due to their conjugated structure and polar structure. By having a donor moiety with a specific structure containing a specific atom as represented by formula (1), the specific compound suppresses excessive aggregation between specific compounds in the photoelectric conversion film, thereby achieving efficient charge separation. As a result, it is believed that a photoelectric conversion element containing the specific compound has an excellent response speed and a small dependency of the response speed on electric field strength. The acceptor moiety also has a specific structure represented by formula (C-1) or (C-2), thereby achieving the same effect as above. Hereinafter, achieving at least one of a better response speed and a smaller dependency of the response speed on the electric field strength is also referred to as "the effect of the present invention being better."

[0024] 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.

[0025] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15. When the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 is applied between the pair of electrodes. －５ ~1 x 10 ７ In terms of performance and power consumption, it is preferable to apply a voltage of 1×10 V / cm. －４ ~1 x 10 ７ V / cm is more preferable, and 1×10 －３ ~5 x 10 ６ V / cm is more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an imaging element, a voltage can be applied in a similar manner. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0026] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film.

[0027] <Specific Compound> The photoelectric conversion film contains a compound (specific compound) represented by formula (1).

[0028]

[0029] In formula (1), X １ and X ２ are each independently -CR ａ１ = or represents a nitrogen atom. ａ１ represents a hydrogen atom or a substituent. ａ１ If there is a plurality of R ａ１ may be the same or different. ３ and X ４ is -C(R ｂ１ R ｂ２ ) -, -O-C(R ｂ３ R ｂ４ ) -, -Si(Rｂ５ R ｂ６ ) -, -Ge(R ｂ７ R ｂ８ ) - or -NR Ｎ１ - represents. ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ , R ｂ６ , R ｂ７ , R ｂ８ and R Ｎ１ R each independently represents a hydrogen atom or a substituent. ｂ１ and R ｂ２ , R ｂ３ and R ｂ４ , R ｂ５ and R ｂ６ , and R ｂ７ and R ｂ８ may be bonded to each other to form a ring which may have a substituent. １ and R ２ each independently represents a hydrogen atom or a substituent. １ and A ２ each independently represents a group represented by formula (C-1) or formula (C-2) described later.

[0030] In formula (1), X １ and X ２ are each independently -CR ａ１ = or represents a nitrogen atom. ａ１ represents a hydrogen atom or a substituent. ａ１ If there is a plurality of R ａ１ may be the same or different. １ and X ２ are each independently, -CR ａ１ It is preferred that R represents ≡ ａ１ Examples of the substituent represented by R include the substituents exemplified above for the substituent W, and more specifically, examples thereof include a halogen atom, an aliphatic hydrocarbon group which may have a substituent, and an aromatic ring group which may have a substituent. ａ１The substituent represented by the formula (I) is preferably a hydrogen atom or an optionally substituted aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms.

[0031] In formula (1), X ３ and X ４ is -C(R ｂ１ R ｂ２ ) -, -O-C(R ｂ３ R ｂ４ ) -, -Si(R ｂ５ R ｂ６ ) -, -Ge(R ｂ７ R ｂ８ ) - or -NR Ｎ１ - represents X ３ and X ４ As -C(R ｂ１ R ｂ２ ) -, -O-C(R ｂ３ R ｂ４ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１ - is preferred, and -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１ - is more preferred, and -C(R ｂ１ R ｂ２ ) - or -NR Ｎ１ - is more preferred. ３ and X ４ -C(R ｂ１ R ｂ２ ) -, -O-C(R ｂ３ R ｂ４ ) - or -NR Ｎ１ In the case of -, the molecular weight is in an appropriate range, and therefore the response speed is superior. ３ and X ４ -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) -, -Ge(R ｂ７ R ｂ８ ) - or -NR Ｎ１When R is -, the heat resistance of the photoelectric conversion element is improved, and the response speed, the electric field strength dependency of the response speed, and the manufacturability are improved. ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ , R ｂ６ , R ｂ７ , R ｂ８ and R Ｎ１ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W described above, and among these, an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent is preferred.

[0032] Examples of the aliphatic hydrocarbon group in the aliphatic hydrocarbon group which may have a substituent include a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms. The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. The branched-chain aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 7 carbon atoms. 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 8 carbon atoms, and even more preferably 3 to 6 carbon atoms.

[0033] The aromatic ring group in the aromatic ring group which may have a substituent may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The aromatic ring group may be either a monocyclic or polycyclic ring. The number of ring members in the aromatic ring group is preferably 5 to 15, more preferably 5 to 10, and even more preferably 5 to 6. The number of carbon atoms in the aromatic ring group which may have a substituent (the number of carbon atoms not including the carbon atoms in the substituent) is preferably 1 to 30, more preferably 3 to 20, and even more preferably 6 to 10. Examples of heteroatoms contained in the aromatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred. Specific examples of the aromatic ring group are as described above, with a phenyl group, a thiophene ring group, or a pyridine ring group being preferred, a phenyl group or a thiophene ring group being more preferred, and a phenyl group being even more preferred. When the aromatic ring group has a substituent, the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

[0034] Examples of the substituent that the aliphatic hydrocarbon group and aromatic ring group may have include the substituents exemplified above for the substituent W, and preferred are substituents selected from the substituent group T. Substituent group T: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms, and cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms. In the substituent group T, the aliphatic hydrocarbon group may have a halogen atom.

[0035] R ｂ１ and R ｂ２ , R ｂ３ and R ｂ４ , R ｂ５ and R ｂ６ , and R ｂ７ and R ｂ８ may be bonded to each other to form a ring which may have a substituent. The ring may be either an aromatic ring or an aliphatic hydrocarbon ring, but an aliphatic hydrocarbon ring is preferred. The ring may be either a monocyclic ring or a polycyclic ring. Examples of the ring include a cyclopentane ring and a cyclohexane ring.

[0036] R ｂ１ and R ｂ２ At least one of R preferably represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, and more preferably represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. ｂ１ and R ｂ２ and R preferably represent an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. ｂ３ and R ｂ４ At least one of R preferably represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, and more preferably represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. ｂ３ and R ｂ４ and R preferably represent an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. ｂ５ and R ｂ６ At least one of R preferably represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, and more preferably represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. ｂ５ and R ｂ６ and R preferably represent an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. ｂ７ and R ｂ８ At least one of R preferably represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, and more preferably represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. ｂ７ and R ｂ８ and R preferably represent an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. Ｎ１ preferably represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, and more preferably represents an aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a substituent, or an aromatic ring group having 6 to 10 carbon atoms which has a substituent.

[0037] In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W. In terms of the effects of the present invention being more excellent, R １ and R ２ is preferably a hydrogen atom.

[0038] In formula (1), A １ and A ２ each independently represents a group represented by formula (C-1) or formula (C-2). The group represented by formula (C-1) will be described in detail below.

[0039]

[0040] In formula (C-1), X ｃ１ ~X ｃ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｚ１ , or =CR Ｚ２ R Ｚ３ Represents R Ｚ１ represents a hydrogen atom or a substituent. Ｚ２ and R Ｚ３ each independently represents a cyano group, —SO ２ R Ｚ４ , -COOR Ｚ５ , or -COR Ｚ６ Represents R Ｚ４ , R Ｚ５ and 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. ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent.

[0041] In formula (C-1), X ｃ１ ~X ｃ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｚ１ , or =CR Ｚ２ R Ｚ３In order to achieve the effects of the present invention more effectively, it is preferable that the specific compound satisfies at least one of the following requirements 1 and 2, and it is more preferable that the specific compound satisfies requirement 1. Requirement 1: In formula (C-1), X ｃ１ and X ｃ３ each independently represents an oxygen atom. ｃ２ represents an oxygen atom.

[0042] R Ｚ１ represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified above for the substituent W. Ｚ２ and R Ｚ３ each independently represents a cyano group, —SO ２ R Ｚ４ , -COOR Ｚ５ , or -COR Ｚ６ Represents R Ｚ４ , R Ｚ５ and R Ｚ６ R each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. The aliphatic hydrocarbon group is defined as above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The aromatic ring group is defined as above, and an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. The aliphatic heterocyclic group is defined as above, and the heteroatom contained in the aliphatic heterocyclic group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. R Ｚ４ , R Ｚ５ and R Ｚ６ Examples of the substituent that each group represented by the following formula may have include the substituents exemplified for the substituent W above.

[0043] In formula (C-1), R ｃ１ and R ｃ２each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent W above, with an aliphatic hydrocarbon group or an aryl group being preferred, and an aliphatic hydrocarbon group being more preferred. The aliphatic hydrocarbon group may be linear, branched, or cyclic, with a linear group being preferred. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 to 2. The aryl group may be monocyclic or polycyclic, with a phenyl group being preferred. The aryl group may further have a substituent, and examples of the substituent include the groups exemplified for the substituent W above. R ｃ１ and R ｃ２ It is preferable that at least one of the groups represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms.

[0044] Next, the group represented by formula (C-2) will be described in detail.

[0045]

[0046] In formula (C-2), X ｃ４ and X ｃ５ R each independently represents an oxygen atom or a sulfur atom. ｃ３ and R ｃ４ each independently represents a hydrogen atom or a substituent.

[0047] In formula (C-2), X ｃ４ and X ｃ５ each independently represents an oxygen atom or a sulfur atom. The halogen atom is preferably a fluorine atom or a chlorine atom.

[0048] R ｃ３ and R ｃ４ R each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified as the substituent W. Among these, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogen atom, or a cyano group is preferred as the substituent. ｃ３ and R ｃ４ Preferably, at least one of R represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a substituent, and R ｃ３ and R ｃ４It is more preferable that at least one of the groups represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent.

[0049] Specific examples of the specific compounds are shown below, but the present invention is not limited to these. １ and A ２ Represents a configuration other than.

[0050]

[0051]

[0052]

[0053]

[0054] The following is a list of specific compounds: １ and A ２ A specific example is shown below.

[0055]

[0056] The molecular weight of the specific compound is preferably 450 to 900, more preferably 450 to 800, and even more preferably 450 to 700. 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.

[0057] 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.

[0058] The maximum absorption wavelength of the specific compound is preferably in the wavelength range of 450 to 800 nm, more preferably in the range of 550 to 700 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the specific compound is insoluble in chloroform, the maximum absorption wavelength of the specific compound is determined by evaporating the specific compound and measuring the value using the specific compound in a film state.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] <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.

[0063] 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.

[0064] 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.

[0065] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0066] 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.

[0067] The photoelectric conversion film preferably has a bulk heterostructure formed by mixing the compound represented by formula (1) (specific compound) with 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.

[0068] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0069] 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%.

[0070] 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.

[0071] 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.

[0072] <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.

[0073] 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 smaller ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are listed below.

[0074]

[0075]

[0076]

[0077]

[0078] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0079] 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%.

[0080] 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.

[0081] <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, and benzophenone dyes. Cridinone 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 2023-010305, and JP 2023-010299, 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, organic dyes, cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred because they have a maximum absorption wavelength in the preferred range described below.

[0082] 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 450 to 650 nm.

[0083] 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%.

[0084] <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.

[0085] 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.

[0086] [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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] [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.

[0091] [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.

[0092] 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.

[0093] [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.

[0094] 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.

[0095] 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.

[0096] [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.

[0097] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. The performance of photoelectric conversion materials may be significantly degraded in the presence of degrading factors such as water molecules. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of ceramics such as dense metal oxides, metal nitrides, or metal nitride oxides, or diamond-like carbon (DLC), which do not allow water molecules to penetrate. Examples of sealing layers include those described in paragraphs

[0210] to

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

[0098] [Method for manufacturing photoelectric conversion element] Examples of methods for manufacturing photoelectric conversion elements include known manufacturing methods. Specifically, for example, a method for manufacturing a photoelectric conversion element includes a step of forming a conductive film on a substrate, a step of forming a photoelectric conversion film, and a step of forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer) in addition to the above. The method for forming each layer is as described above.

[0099] [Image capture element] An example of an application of a photoelectric conversion element is an image capture element. An image capture 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 image capture element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0100] [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.

[0101] [Compound] The present invention also includes the invention of a compound. The compound of the present invention is the above-mentioned specific compound (compound represented by formula (1)).

[0102] 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.

[0103] [Compounds used in photoelectric conversion film] The materials used in the photoelectric conversion film are shown below.

[0104] [Synthesis of Compound (1-1)] Compound (1-1) was synthesized according to the following scheme.

[0105]

[0106] <Synthesis of Compound (1-1-2)> After replacing the atmosphere in a glass reaction vessel with nitrogen, 10 mmol of compound (1-1-1) and 100 ml of dehydrated tetrahydrofuran (THF) were added and cooled to -78°C. 21 mmol of n-BuLi was added dropwise to this mixture at -60°C or below, and the reaction solution was stirred for 10 minutes. 22 mmol of dehydrated dimethylformamide (DMF) was then added dropwise at -60°C or below, and the temperature was raised to room temperature. An aqueous ammonium chloride solution was added to the reaction solution, and the precipitated solid was collected by filtration. The collected solid was purified by silica gel column chromatography to obtain 7.5 mmol of compound (1-1-2) (yield 75%).

[0107] <Synthesis of Compound (1-1)> 2 mmol of compound (1-1-2), 5.0 mmol of 1,3-dimethylbarbituric acid, 60 mL of toluene, and 0.4 mmol of piperidine were placed in a glass reaction vessel and reacted at 100°C for 2 hours under a nitrogen atmosphere. The precipitated solid was filtered, and the resulting solid was washed successively with tetrahydrofuran (THF), dimethylacetamide, and THF, and then purified by sublimation to obtain 1.3 mmol of compound (1-1) (yield: 65%). The structure of compound (1-1) was confirmed by LDI-MS (laser desorption ionization mass spectrometry). The results of LDI-MS measurement of compound (1-1) are shown below. LDI-MS (compound (1-1)): 604 (M ＋ )

[0108] The compounds used in the photoelectric conversion film of each of the Examples and Comparative Examples other than the compound (1-1) were synthesized according to the synthesis method of the compound (1-1).

[0109] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for comparison are shown below. Note that compounds (1-1) to (1-28) are specific compounds, and compounds (2-1) to (2-4) are comparative compounds.

[0110]

[0111]

[0112] [n-type organic semiconductor] Fullerene (C ６０ )

[0113] [p-type organic semiconductor]

[0114]

[0115] [Evaluation] The photoelectric conversion element was evaluated for quantum efficiency when receiving red light (wavelength 650 nm), response speed, electric field strength dependency of response speed, and manufacturability by the following methods.

[0116] [Fabrication of Photoelectric Conversion Element] A photoelectric conversion element having the configuration shown in FIG. 2 was fabricated using the various components shown above. Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Subsequently, with the glass substrate at room temperature, each specific compound or each comparative compound shown in Table 1 and an n-type organic semiconductor (fullerene (C ６０ )) and a p-type organic semiconductor (D-1) were co-deposited by vacuum deposition to form a film having a thickness of 80 nm in terms of a single layer. This resulted in a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. At this time, the film formation rate of the photoelectric conversion film 12 was 1.0 Å / sec. Furthermore, a compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After a SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al ２ O ３ The resulting laminate was heated in a glove box at 150° C. for 30 minutes to obtain a photoelectric conversion element.

[0117]

[0118] [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.

[0119] [Quantum Efficiency] The quantum efficiency of each photoelectric conversion element was measured when red 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 measure the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 650 nm. As a result, it was confirmed that the external quantum efficiency was 50% or more in all photoelectric conversion elements.

[0120] [Response Speed] The response speed of each photoelectric conversion element when receiving red light was evaluated by the following method. ５ A voltage was applied so that the intensity was 1000 V / cm. Thereafter, an LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 650 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 (S1). From the obtained value, the response speed was evaluated according to the following evaluation criteria. The response speed is preferably evaluated as C or higher. Formula (S1): Relative response speed = (rise time of each photoelectric conversion element) / rise time of the photoelectric conversion element of Example 6

[0121] A: Relative response speed is less than 1.0 B: Relative response speed is 1.0 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

[0122] [Dependence of response speed on electric field strength] The dependence of the response speed on electric field strength when red light was received was evaluated for each photoelectric conversion element by the following method. In the evaluation of the response speed, a voltage of 7.5×10 was applied to each photoelectric conversion element. ４ The same procedure was followed except that the pressure was changed to 7.5 × 10 ４ The rise time at 7.5 V / cm was measured. The electric field strength dependency of the response speed was calculated according to formula (S2), and the electric field strength dependency of the response speed was evaluated according to the following evaluation criteria. In formula (S2), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. The electric field strength dependency of the response speed is preferably rated C or higher. Formula (S2): Electric field strength dependency of response speed = (applied voltage of each photoelectric conversion element 7.5 × 10 ４ V / cm) / (applied voltage of each photoelectric conversion element 2.0×10 ５ rise time in V / cm)

[0123] A: The electric field strength dependency of the response speed is less than 3.0. B: The electric field strength dependency of the response speed is 3.0 or more and less than 4.0. C: The electric field strength dependency of the response speed is 4.0 or more and less than 5.0. D: The electric field strength dependency of the response speed is 5.0 or more.

[0124] [Manufacturing Suitability] The manufacturability of each photoelectric conversion element was evaluated using the following method. Photoelectric conversion elements (B) of each Example or Comparative Example were fabricated using the same procedure as in the above [Fabrication of Photoelectric Conversion Elements], except that the deposition rate of the photoelectric conversion film 12 was set to 3.0 Å / sec. The quantum efficiency (photoelectric conversion efficiency) of the resulting photoelectric conversion elements (B) was measured using the same method as in the above [Quantum Efficiency]. The photoelectric conversion element obtained in the above [Fabrication of Photoelectric Conversion Elements], in which the deposition rate of the photoelectric conversion film 12 was 1.0 Å / sec, was designated as photoelectric conversion element (A), and the relative ratio B / A of quantum efficiency (photoelectric conversion efficiency) was calculated according to formula (S3). From the obtained values, the manufacturability was evaluated according to the following evaluation criteria. In formula (S3), the photoelectric conversion elements (B) and (A) in the numerator and denominator are photoelectric conversion elements fabricated using the same material. The closer the value of the relative ratio B / A is to 1, the less the performance of the photoelectric conversion element is likely to deteriorate even when the film formation rate is increased, i.e., the better the manufacturability. The manufacturability is preferably evaluated as C or higher. Formula (S3): Relative ratio B / A = (photoelectric conversion efficiency of photoelectric conversion element (B)) / (photoelectric conversion efficiency of photoelectric conversion element (A))

[0125] A: The relative ratio B / A is 0.90 or more. B: The relative ratio B / A is 0.85 or more and less than 0.90. C: The relative ratio B / A is 0.80 or more and less than 0.85. D: The relative ratio B / A is less than 0.80.

[0126] [Results] The evaluation results are shown in Table 1 below. ｂ " column indicates the R ｂ１ and R ｂ２ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ７ and R ｂ８ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; Ｎ１represents an aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a substituent, or an aromatic ring group having 6 to 12 carbon atoms which may have a substituent, it is designated as "A", and in other cases it is designated as "B". ３ and X ４ are each independently -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１ In the "C, N" column, X is used for a specific compound. ３ and X ４ are each independently -C(R ｂ１ R ｂ２ ) - or -NR Ｎ１ When it represents -, it is written as "A", and when it represents anything other than the above, it is written as "B". ａ１ " column is for specific compounds, X １ and X ２ are each independently -CR ａ１ In the table, "R" is used to indicate that the value is equal to or greater than the above, and "B" is used in other cases. ｃ " column indicates the specific compound in formula (C-1), R ｃ１ and R ｃ２ At least one of R independently represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and in formula (C-2), ｃ３ and R ｃ４ When at least one of the above represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent, it is designated as "A", and in other cases it is designated as "B". ｃ１ ,X ｃ３ " column indicates the specific compound in formula (C-1), X ｃ１ and X ｃ３ are each independently represented by "A" when they represent an oxygen atom, and "B" when they are not represented by the above. ｃ２ " column indicates the specific compound in formula (C-1), X ｃ２ represents an oxygen atom, it is designated as "A", and in other cases it is designated as "B".

[0127]

[0128] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention has an excellent response speed when receiving red light and has a small dependency of the response speed on the electric field strength. It was also confirmed that the photoelectric conversion element of the present invention has excellent manufacturability when receiving red light.

[0129] From comparisons between Examples 1 to 8, Example 14, and Example 28, it is clear that in formula (C-1), R ｃ１ and R ｃ２ At least one of R independently represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and in formula (C-2), ｃ３ and R ｃ４ It was confirmed that when at least one of the groups represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent, the response speed, the electric field strength dependency of the response speed, and the manufacturing suitability are better. ｃ２ It was confirmed that when X represents an oxygen atom, the manufacturing suitability is better. ｃ１ and X ｃ３ and each independently represent an oxygen atom, it was confirmed that the response speed, the electric field strength dependency of the response speed, and the manufacturability were better. １ and X ２ are each independently -CR ａ１ It was confirmed that when X = 1, the response speed, the electric field strength dependency of the response speed, and the manufacturability were better. ３ and X ４ But -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１ When X represents -, the response speed, the electric field strength dependency of the response speed, and the manufacturability are better. ３ and X ４ But -C(R ｂ１ R ｂ２ ) - or -NR Ｎ１It was confirmed that when R represents -, the response speed, the electric field strength dependency of the response speed, and the manufacturability were further improved. ｂ１ and R ｂ２ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ７ and R ｂ８ at least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; Ｎ１ represents an aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a substituent, or an aromatic ring group having 6 to 12 carbon atoms which may have a substituent, it has been confirmed that the response speed, the electric field strength dependency of the response speed, and the manufacturing suitability are better.

[0130] 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), X １ and X ２ Each independently represents -CR ａ１ = or a nitrogen atom. ａ１ represents a hydrogen atom or a substituent. ａ１ If there are multiple R ａ１ may be the same or different. ３ and X ４ is -C(R ｂ１ R ｂ２ ) -, -O-C(R ｂ３ R ｂ４ ) -, -Si(R ｂ５ R ｂ６ ) -, -Ge(R ｂ７ R ｂ８ ) - or -NR Ｎ１ - represents. ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ , R ｂ６ , R ｂ７ , R ｂ８ and R Ｎ１ R each independently represents a hydrogen atom or a substituent. ｂ１ and R ｂ２ , R ｂ３ and R ｂ４ , R ｂ５ and R ｂ６ , and R ｂ７ and R ｂ８ may be bonded to each other to form a ring which may have a substituent. １ and R ２ each independently represents a hydrogen atom or a substituent. １ and A ２ Each of X independently represents a group represented by formula (C-1) or formula (C-2). ｃ１ ~X ｃ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｚ１ , or = CR Ｚ２ R Ｚ３ Represents Ｚ１ represents a hydrogen atom or a substituent. Ｚ２ and R Ｚ３ each independently represents a cyano group, —SO ２ R Ｚ４ , -COOR Ｚ５ , or -COR Ｚ６ Represents Ｚ４ , R Ｚ５ and 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. ｃ１ and R ｃ２ Each of X independently represents a hydrogen atom or a substituent. ｃ４ and X ｃ５ R each independently represents an oxygen atom or a sulfur atom. ｃ３ and R ｃ４ each independently represents a hydrogen atom or a substituent. * represents a bonding position.

2. R ｂ１ and R ｂ２ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ７ and R ｂ８ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; Ｎ１ The photoelectric conversion element according to claim 1 , wherein represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent.

3. R ｂ１ and R ｂ２ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ３ and R ｂ４ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ５ and R ｂ６ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ７ and R ｂ８ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; Ｎ１ 2. The photoelectric conversion element according to claim 1, wherein represents an aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a substituent, or an aromatic ring group having 6 to 10 carbon atoms which has a substituent.

4. In the formula (1), X ３ and X ４ Each independently represents -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１ The photoelectric conversion element according to claim 1 , 5. In the formula (1), X ３ and X ４ Each independently represents -C(R ｂ１ R ｂ２ ) - or -NR Ｎ１ The photoelectric conversion element according to claim 4 , wherein 6. In the formula (1), X １ and X ２ Each independently represents -CR ａ１ The photoelectric conversion element according to claim 1 , wherein:

7. In the formula (C-1), R ｃ１ and R ｃ２ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms, ｃ３ and R ｃ４ 2. The photoelectric conversion element according to claim 1, wherein at least one of the groups represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent.

8. The photoelectric conversion element according to claim 1, wherein the compound represented by formula (1) satisfies at least one of requirements 1 and 2. Requirement 1: In the formula (C-1), X ｃ１ and X ｃ３ Each of X independently represents an oxygen atom. ｃ２ represents an oxygen atom.

9. The photoelectric conversion element according to claim 8, wherein the compound represented by formula (1) satisfies requirement 1.

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

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

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

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

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

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

16. An optical sensor comprising the photoelectric conversion element according to any one of claims 1 to 14.

17. A method for manufacturing an imaging element, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 14.

18. A compound represented by formula (1). In formula (1), X １ and X ２ Each independently represents -CR ａ１ = or a nitrogen atom. ａ１ represents a hydrogen atom or a substituent. ａ１ If there are multiple R ａ１ may be the same or different. ３ and X ４ is -C(R ｂ１ R ｂ２ ) -, -O-C(R ｂ３ R ｂ４ ) -, -Si(R ｂ５ R ｂ６ ) -, -Ge(R ｂ７ R ｂ８ ) - or -NR Ｎ１ - represents. ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ , R ｂ６ , R ｂ７ , R ｂ８ and R Ｎ１ R each independently represents a hydrogen atom or a substituent. ｂ１ and R ｂ２ , R ｂ３ and R ｂ４ , R ｂ５ and R ｂ６ , and R ｂ７ and R ｂ８ may be bonded to each other to form a ring which may have a substituent. １ and R ２ each independently represents a hydrogen atom or a substituent. １ and A ２ Each of X independently represents a group represented by formula (C-1) or formula (C-2). ｃ１ ~X ｃ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｚ１ , or = CR Ｚ２ R Ｚ３ Represents Ｚ１ represents a hydrogen atom or a substituent. Ｚ２ and R Ｚ３ each independently represents a cyano group, —SO ２ R Ｚ４ , -COOR Ｚ５ , or -COR Ｚ６ Represents Ｚ４ , R Ｚ５ and 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. ｃ１ and R ｃ２ Each of X independently represents a hydrogen atom or a substituent. ｃ４ and X ｃ５ R each independently represents an oxygen atom or a sulfur atom. ｃ３ and R ｃ４ each independently represents a hydrogen atom or a substituent. * represents a bonding position.

19. R ｂ１ and R ｂ２ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ３ and R ｂ４ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ５ and R ｂ６ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; ｂ７ and R ｂ８ at least one of R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent; Ｎ１ The compound according to claim 18 , wherein represents an optionally substituted aliphatic hydrocarbon group, or an optionally substituted aromatic ring group.

20. R ｂ１ and R ｂ２ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ３ and R ｂ４ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ５ and R ｂ６ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; ｂ７ and R ｂ８ At least one of R represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent; Ｎ１ represents an optionally substituted aliphatic hydrocarbon group having 3 to 4 carbon atoms, or a substituted aromatic ring group having 6 to 10 carbon atoms.

21. In the above formula (1), X ３ and X ４ Each independently represents -C(R ｂ１ R ｂ２ ) -, -Si(R ｂ５ R ｂ６ ) - or -NR Ｎ１ The compound according to claim 18, wherein 22. In the formula (1), X ３ and X ４ Each independently represents -C(R ｂ１ R ｂ２ ) - or -NR Ｎ１ The compound according to claim 21, wherein 23. In the formula (1), X １ and X ２ Each independently represents -CR ａ１ 20. The compound according to claim 18, wherein:

24. In the formula (C-1), R ｃ１ and R ｃ２ At least one of R independently represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms, ｃ３ and R ｃ４ The compound according to any one of claims 18 to 23, wherein at least one of the following represents an aliphatic hydrocarbon group having 1 to 2 carbon atoms which may have a substituent.

25. The compound according to any one of claims 18 to 23, wherein the compound represented by formula (1) satisfies at least one of requirements 1 and 2. Requirement 1: In the formula (C-1), X ｃ１ and X ｃ３ Each of X independently represents an oxygen atom. ｃ２ represents an oxygen atom.

26. The compound according to claim 25, wherein the compound represented by formula (1) satisfies requirement 1.

Images