Photoelectric conversion element, imaging element, optical sensor, and method for producing imaging element

Abstract

The present invention addresses the problem of providing a photoelectric conversion element in which the electric field dependence of the quantum efficiency when blue-green light is received is low, and the electric field dependence of the quantum efficiency when green-red light is received is low. A photoelectric conversion element according to the present invention has a conductive film, a photoelectric conversion film, and a transparent conductive film in this order. The photoelectric conversion film contains a compound represented by formula (1) or (2) and a compound represented by formula (3).

Description

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

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

[0002] In recent years, development of devices (e.g., imaging devices) having a photoelectric conversion film has progressed. For example, Patent Document 1 discloses a photoelectric conversion device having a photoelectric conversion film containing a specific compound.

[0003] International Publication No. 2023 / 171788

[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. For example, the characteristics required of a photoelectric conversion element include a requirement that the quantum efficiency of the photoelectric conversion element is resistant to change even when the electric field strength is changed, i.e., that the quantum efficiency has a small electric field strength dependency. Furthermore, depending on the application of the photoelectric conversion element, it is desirable that the photoelectric conversion element exhibit excellent characteristics over a wide wavelength range. In response to such demands, the present inventors fabricated and examined the photoelectric conversion element disclosed in Patent Document 1 and found that the electric field strength dependency of the quantum efficiency when receiving blue-green light and the electric field strength dependency of the quantum efficiency when receiving green-red light did not meet the desired level, leaving room for improvement. Note that the blue-green light refers to light with a wavelength of 400 to 560 nm, and the green-red light refers to light with a wavelength of 500 to 700 nm.

[0005] Therefore, an object of the present invention is to provide a photoelectric conversion element that has a small electric field strength dependency of quantum efficiency when receiving blue-green light and a small electric field strength dependency of quantum efficiency when receiving green-red light. Another object of the present invention is to provide an imaging element, an optical sensor, and a method for manufacturing an imaging element 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 first compound represented by Formula (1) or Formula (2) described later, and a second compound represented by Formula (3) described later. [2] The photoelectric conversion element according to [1], wherein the photoelectric conversion film has a mixed layer formed by mixing the first compound and the second compound. [3] The photoelectric conversion element according to [2], wherein the mixed layer further contains an n-type organic semiconductor, and has a bulk heterostructure formed by mixing the first compound, the second compound, and the n-type organic semiconductor. [4] The photoelectric conversion element according to [3], wherein the mixed layer further contains a p-type organic semiconductor, and has a bulk heterostructure formed by mixing the first compound, the second compound, the n-type organic semiconductor, and the p-type organic semiconductor. [5] The photoelectric conversion element according to [3] or [4], wherein the n-type organic semiconductor comprises a fullerene selected from the group consisting of fullerenes and derivatives thereof. [6] The photoelectric conversion element according to [1], wherein the photoelectric conversion film has a first layer comprising the first compound and a second layer comprising the second compound. [7] The photoelectric conversion element according to [6], wherein the first layer and the second layer further comprise an n-type organic semiconductor, the first layer has a bulk heterostructure formed in a state where the first compound and the n-type organic semiconductor are mixed, and the second layer has a bulk heterostructure formed in a state where the second compound and the n-type organic semiconductor are mixed. [8] The photoelectric conversion element according to [7], wherein the first layer and the second layer further contain a p-type organic semiconductor, the first layer has a bulk heterostructure formed in a state where the first compound, the n-type organic semiconductor, and the p-type organic semiconductor are mixed, and the second layer has a bulk heterostructure formed in a state where the second compound, the n-type organic semiconductor, and the p-type organic semiconductor are mixed. [9] The photoelectric conversion element according to [7] or [8], wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof.

[10] The photoelectric conversion element according to any one of [1] to [9], wherein the content of the first compound relative to the content of the second compound in the photoelectric conversion film is 40 to 240 volume %.

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

[10] , wherein the first compound has an absorption maximum in a wavelength range of 400 to 500 nm, and the second compound has an absorption maximum in a wavelength range of 500 to 650 nm.

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

[11] , wherein the compound represented by formula (1) is a compound represented by formula (4) described below, and the compound represented by formula (2) is a compound represented by formula (5) described below.

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

[12] , wherein in formula (3), n is 1.

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

[13] , wherein in formula (D-1), k is 1 or 2.

[15] In the above formula (3), A. ３１ and A ３２ each independently represent a group represented by formula (A-1) above.

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

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

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

[16] .

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

[16] .

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

[16] .

[0008] According to the present invention, a photoelectric conversion element can be provided in which the quantum efficiency when blue-green light is received has a small electric field strength dependency, and when green-red light is received has a small electric field strength dependency. Furthermore, according to the present invention, an imaging element, an optical sensor, and a method for manufacturing an imaging element related to the photoelectric conversion element can 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] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] In this specification, a hydrogen atom may be either a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom). In this specification, when there are multiple substituents, 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, this 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.

[0013] In this specification, unless otherwise specified, examples of the "substituent" include the groups exemplified as the substituent W below.

[0014] (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 aryloxycarbonyloxy group, Examples of the substituent W include primary, secondary, or tertiary amino groups (including anilino groups), alkylthio groups, arylthio groups, heterocyclic thio groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, aryl or heterocyclic azo groups, imido groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, carboxy groups, phosphate groups, sulfonic acid groups, hydroxy groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, and boronic acid groups. Each of the above groups may further have a substituent (e.g., one or more of the above groups) if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. When the substituent W has carbon atoms, 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 phosphate 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 does not have a primary amino group.

[0015] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0016] In this specification, unless otherwise specified, 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. 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. Unless otherwise specified, 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 sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclopropyl group, and a cyclopentyl group. The cyclic alkyl group may be a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and the alkyl group 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 and 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). 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) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6) condensed aromatic ring structures as a ring structure. The number of ring member atoms of the aromatic ring is preferably 5 to 15. In this specification, unless otherwise specified, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. When the aromatic ring is an aromatic heterocyclic ring, the number of heteroatoms 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- b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, and 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc.), benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring, and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring.

[0020] In this specification, the term "aromatic ring group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic ring. In this specification, the term "aromatic hydrocarbon group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic hydrocarbon ring, and the term "aromatic heterocyclic group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic heterocycle. In this specification, the term "aryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to the aromatic hydrocarbon ring of the above-mentioned aromatic ring. In this specification, the term "heteroaryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to the aromatic heterocycle of the above-mentioned aromatic ring. In this specification, the term "arylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to the aromatic hydrocarbon ring of the above-mentioned aromatic ring. In this specification, the term "heteroarylene group" refers to, 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 group, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted arylene group, and optionally substituted heteroarylene group, the types of substituents that these groups may have include, for example, the groups exemplified for the substituent W. When these groups have substituents, the number of substituents may be 1 or more (for example, 1 to 4, etc.).

[0021] As used herein, the term "aliphatic ring" refers to a ring structure that does not fall under the category of aromatic rings, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle. Examples of the aliphatic hydrocarbon ring include a cycloalkane, a cycloalkene, and a cycloalkyne. Examples of the aliphatic heterocycle include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane 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. As used herein, the term "aliphatic hydrocarbon ring group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that falls under the category of an aliphatic hydrocarbon ring. As used herein, the term "aliphatic heterocyclic group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that falls under the category of an aliphatic heterocycle.

[0022] In this specification, when a formula showing a chemical structure contains a plurality of identical symbols indicating the type or number of groups, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different, unless otherwise specified. In this specification, when a formula showing a chemical structure contains a plurality of groups of the same type (e.g., alkyl groups, etc.), the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the plurality of groups of the same type may be the same or different, unless otherwise specified.

[0023] In this specification, the bonding direction of a divalent group (e.g., -CO-O-, etc.) is not limited unless otherwise specified. 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."

[0024] In this specification, with respect to compounds that may have geometric isomers (cis-trans isomers), the general formula or structural formula representing the compound may 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. Furthermore, in this specification, with respect to compounds having an asymmetric atom, the general formula or structural formula representing the compound may be described without distinguishing between stereoisomers for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either form, and may be any one form or a mixture. For example, a compound having an asymmetric carbon atom may be either the S-form or the R-form, or a mixture thereof, unless otherwise specified.

[0025] In this specification, unless otherwise specified, * in a formula indicates a bonding position.

[0026] [Photoelectric conversion element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a first compound represented by the formula (1) described later or the formula (2) described later, and a second compound represented by the formula (3) described later.

[0027] Although the reason why the photoelectric conversion element having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The first compound is a so-called DA-type dye compound having a donor moiety and an acceptor moiety. As a DA-type dye compound, by combining a specific donor moiety having a bulky substituent with a specific compact acceptor moiety, it is possible to reduce intermolecular interactions due to the structure and molecular weight, and to suppress excessive aggregation in the photoelectric conversion film. Furthermore, the second compound is a so-called ADA-type dye compound having acceptor moieties at both ends and a donor moiety in the center. As an ADA-type dye compound, it is speculated that the donor moiety has a fused ring structure, which suppresses structural changes during charge transfer, enabling efficient charge transfer. Because the photoelectric conversion film contains a first compound in which excessive aggregation is suppressed and a second compound capable of efficient charge transfer, these compounds act cooperatively within the photoelectric conversion film to appropriately adjust the aggregation and interaction between the compounds, enabling smooth charge transfer. As a result, it is believed that the electric field strength dependence of the quantum efficiency when blue-green light and green-red light are received is small. Hereinafter, achieving at least one of smaller electric field strength dependence when blue-green light is received and smaller electric field strength dependence when green-red light is received is also referred to as "excellent effects of the present invention."

[0028] The photoelectric conversion film has a first compound and a second compound. The photoelectric conversion film is not particularly limited as long as it has the first compound and the second compound, but is preferably an embodiment having a mixed layer formed in a state in which the first compound and the second compound are mixed (hereinafter also referred to as the "first embodiment of the photoelectric conversion film"), or an embodiment having a first layer containing the first compound and a second layer containing the second compound (hereinafter also referred to as the "second embodiment of the photoelectric conversion film"). Hereinafter, when simply referring to the "photoelectric conversion film", it includes both the first embodiment of the photoelectric conversion film and the second embodiment of the photoelectric conversion film.

[0029] 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 11 functioning as a lower electrode (hereinafter also referred to as the "lower electrode"), an electron blocking film 16A, a photoelectric conversion film 12, and a transparent conductive film 15 functioning as an upper electrode (hereinafter also referred to as the "upper electrode") are stacked in this order. FIG. 2 shows another example of the configuration of a 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 the lower electrode 11. 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. In the photoelectric conversion film 12, the photoelectric conversion film 12 of the first embodiment has a mixed layer containing a first compound and a second compound. The photoelectric conversion element 12 of the second embodiment has a configuration in which a first layer containing a first compound and a second layer containing a second compound are stacked. In the photoelectric conversion element 12 of the second embodiment, the stacking order of the first layer and the second layer can be appropriately selected depending on the application and characteristics.

[0030] 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 ６V / 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.

[0031] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film, which contains a first compound and a second compound. The first compound and the second compound will be described in detail below.

[0032] <First Compound> The photoelectric conversion film contains a first compound which is a compound represented by formula (1) or formula (2).

[0033]

[0034] In formula (1), R １１ and R １２ R each independently represents a hydrogen atom or a substituent. ａ１１ and R ａ１２ each independently represents an optionally substituted aryl group, —C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ), or a heteroaryl group which may have a substituent. Ｌ１１ ~R Ｌ１３ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, provided that R Ｌ１１ ~R Ｌ１３ At least two of R represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Ｌ１１ ~R Ｌ１３The optionally substituted alkyl group, the optionally substituted aryl group, and the optionally substituted heteroaryl group represented by the following formula (I) may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. １１ represents an aromatic ring which may have a substituent. ２１ and R ２２ R each independently represents a hydrogen atom or a substituent. ２３ and R ２４ R each independently represents a substituent. ２３ and R ２４ may be bonded to each other to form a ring which may have a substituent. ａ２ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ２１ represents an aromatic ring which may have a substituent. ２１ represents a monocyclic ring having 5 or more ring atoms, which may have a substituent. ２１ and Z ２２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｙ１ , or =CR Ｙ２ R Ｙ３ Represents R Ｙ１ represents a hydrogen atom or a substituent. Ｙ２ and R Ｙ３ each independently represents a cyano group, —COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ Represents R Ｙ４ ~R Ｙ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

[0035] In formula (1), R １１ and R １２ R each independently represents a hydrogen atom or a substituent. １１ and R １２Examples of the substituent represented by the formula (I) include the substituent W described above, and a hydrogen atom is preferred in terms of achieving better effects of the present invention.

[0036] In formula (1), R ａ１１ and R ａ１２ each independently represents an optionally substituted aryl group, —C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ), or a heteroaryl group which may have a substituent. ａ１１ and R ａ１２ As the alkyl group, an aryl group which may have a substituent or —C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ) is preferable, an aryl group which may have a substituent is more preferable, and a group represented by formula (Z) described below is even more preferable. ａ１１ and R ａ１２ When each of R represents an aryl group which may have a substituent, R ａ１１ and R ａ１２ It is preferable that at least one of R represents a group represented by formula (Z). ａ１１ and R ａ１２ It is preferable that at least one of R is a group represented by formula (Z). ａ１１ and R ａ１２ are also preferably different groups.

[0037] R ａ１１ and R ａ１２The aryl group represented by the formula (I) may be either monocyclic or polycyclic. The number of ring atoms in the aryl group is preferably 6 to 12, more preferably 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, an anthryl group, or a fluorenyl group, and more preferably a phenyl group. Substituents that the aryl group may have include the substituent W described above, and are preferably an alkyl group, an aryl group, a heteroaryl group, a cyano group, or a halogen atom, more preferably an alkyl group or a halogen atom, and even more preferably an alkyl group having 2 or more carbon atoms. The alkyl group exemplified as a substituent that the aryl group may have may be linear, branched, or cyclic, and branched is preferred in terms of better quantum efficiency. The number of carbon atoms in the alkyl group is preferably 2 or more in terms of better quantum efficiency. The upper limit is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. When the aryl group has a substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2 or 3. Among these, the aryl group is preferably a group represented by formula (Z).

[0038]

[0039] In formula (Z), R Ｚ１ ~R Ｚ５ R each independently represents a hydrogen atom or a substituent. Ｚ１ and R Ｚ５ It is preferable that at least one of R Ｚ１ and R Ｚ５ is more preferably a substituent. Ｚ１ ~R Ｚ５ The definition and preferred embodiments of the substituent represented by the formula ａ１１ and R ａ１２ In particular, in terms of being more excellent in quantum efficiency, R Ｚ１ and R Ｚ５ At least one of R is preferably an alkyl group having 2 or more carbon atoms, Ｚ１ and R Ｚ５ is more preferably an alkyl group having two or more carbon atoms.

[0040] R Ｚ１ ~R Ｚ５ When two or more adjacent groups among R represent the above-mentioned substituents, the adjacent substituents may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. Ｚ１ and R Ｚ２ are all substituents, R Ｚ１ and R Ｚ２ and may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. Ｚ２ and R Ｚ３ are all substituents, R Ｚ３ and R Ｚ４ are both substituents, and R Ｚ４ and R Ｚ５ The same applies when all of the groups are substituents. Examples of the divalent linking group include a divalent aliphatic hydrocarbon group (preferably having 1 to 3 carbon atoms), -O-, -CO-, -S-, and -SO ２ - and -NR Ｎ - (R Ｎ is a hydrogen atom or a substituent). The ring is preferably an aliphatic ring. The ring may be either a monocyclic or polycyclic ring. The number of ring atoms in the ring is preferably 3 to 20, more preferably 4 to 12, and even more preferably 4 to 6. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, a nitrogen atom, or an oxygen atom being preferred. Examples of the substituent that the ring may have include the substituent W described above, with an alkyl group, an aryl group, or a halogen atom being preferred.

[0041] R ａ１１ and R ａ１２The heteroaryl group represented by the formula (I) may be either monocyclic or polycyclic. Examples of heteroatoms contained in the heteroaryl group are as described above, and a nitrogen atom, a sulfur atom, or an oxygen atom is preferred. The number of ring atoms in the heteroaryl group is preferably 5 to 20, more preferably 5 to 12. The definition and preferred embodiments of the substituents that the heteroaryl group may have are described in the above R ａ１１ and R ａ１２ The definitions and preferred embodiments of the substituents that the aryl group represented by the following formula (I) may have are the same as those of the substituents that the aryl group represented by the following formula (I) may have.

[0042] -C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ) Medium, R Ｌ１１ ~R Ｌ１３ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, provided that R Ｌ１１ ~R Ｌ１３ At least two of R represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Examples of the substituent which the alkyl group, aryl group, and heteroaryl group may have include the substituent W described above, and an alkyl group, an aryl group, or a halogen atom is preferred. Ｌ１１ ~R Ｌ１３ The alkyl group represented by R may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3. Ｌ１１ ~R Ｌ１３ The definitions and preferred embodiments of the aryl group and heteroaryl group represented by R ａ１１ and R ａ１２ The aryl and heteroaryl groups are the same as those represented by the following formula:

[0043] R Ｌ１１ ~R Ｌ１３The optionally substituted alkyl group, the optionally substituted aryl group, and the optionally substituted heteroaryl group represented by the following formula (I) may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. For example, R Ｌ１１ and R Ｌ１２ and optionally substituted alkyl groups represented by the formula (I) may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent, and R Ｌ１１ an aryl group optionally having a substituent represented by R Ｌ１２ and an alkyl group represented by the formula (I) may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. Examples of the divalent linking group include a divalent hydrocarbon group (e.g., an alkylene group or an arylene group), -O-, -CO-, -SO ２ Examples of the ring include -, -NH-, and groups formed by combining these. The ring is preferably an aliphatic ring. The number of ring atoms in the ring is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, a nitrogen atom, or an oxygen atom being preferred. Examples of the substituent that the ring may have include the substituent W described above, with an alkyl group, an aryl group, or a halogen atom being preferred.

[0044] In formula (1), Ar １１represents an aromatic ring which may have a substituent. The aromatic ring may be either a monocyclic or a polycyclic ring, with a polycyclic ring being preferred in terms of better effects of the present invention. The number of condensed rings in the polycyclic ring is preferably 2 to 4, more preferably 2. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic heterocyclic ring being preferred. Examples of heteroatoms contained in the aromatic heterocyclic ring are as described above, with an oxygen atom, a nitrogen atom, or a sulfur atom being preferred, and a nitrogen atom being more preferred. The number of ring-member atoms in the aromatic ring group is preferably 5 to 20, more preferably 6 to 14, and even more preferably 8 to 10. Among these, a polycyclic ring containing a nitrogen-containing aromatic ring is preferred as the aromatic ring. Examples of the substituent that the aromatic ring may have include the substituent W described above, and are preferably a halogen atom, an optionally substituted aliphatic hydrocarbon group (preferably an alkyl group having 1 to 3 carbon atoms), an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group, an optionally substituted alkoxy group (preferably an alkyl group having 1 to 3 carbon atoms), an optionally substituted acyl group (preferably an acyl group having 2 to 4 carbon atoms), an optionally substituted alkyloxycarbonyl group (preferably an alkyl group having 2 to 4 carbon atoms), a silyl group, a cyano group, or a nitro group, and more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms which may have a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred. The substituent is also preferably a substituent other than a chlorine atom, and more preferably a substituent other than a halogen atom.

[0045] The compound represented by formula (1) is preferably a compound represented by formula (11).

[0046]

[0047] In formula (11), R １１ , R １２ , R ａ１１ , and R ａ１２ is R in formula (1). １１ , R １２ , R ａ１１ , and R ａ１２is synonymous with.

[0048] In formula (11), X １ ~X ４ are each independently -CR ｘ１ = or represents a nitrogen atom. １ ~X ４ At least two of the ｘ１ =, and two are -CR ｘ１ =, and more preferably two are nitrogen atoms, and X ２ and X ３ Ga-CR ｘ１ = and X １ and X ４ It is more preferred that is a nitrogen atom.

[0049] R ｘ１ R each independently represents a hydrogen atom or a substituent. ｘ１ The definition and preferred embodiments of the substituent represented by the formula (1) are as follows: １１ These are the same as the substituents that may be possessed by the aromatic ring represented by R ｘ１ As the substituent represented by the formula: a substituent other than a halogen atom is also preferred.

[0050] X １ ~X ４ Two adjacent ones (e.g., X １ and X ２ , X ２ and X ３ , or X ３ and X ４ ) is -CR ｘ１ If -CR = , two adjacent -CR ｘ１ = contains R ｘ１ may be bonded to each other to form a ring which may have a substituent. ２ and X ３ Ga-CR ｘ１ If =, X ２ R in ｘ１ and X ３ R in ｘ１ and may be bonded to each other to form a ring which may have a substituent. ３ and X ４ Ga-CR ｘ１ = and X１ and X ２ Ga-CR ｘ１ =. The ring may be any of an aromatic ring, an aliphatic ring, and a condensed ring of an aromatic ring and an aliphatic ring, with an aromatic ring being preferred. The ring may be any of a monocyclic ring and a polycyclic ring, with a monocyclic ring being preferred. The number of ring atoms in the ring is preferably 5 to 14, more preferably 6 to 10, and even more preferably 6. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, a nitrogen atom, or an oxygen atom being preferred. Examples and preferred embodiments of the substituent that the ring may have are those of Ar in the above formula (1). １１ These are the same as the substituents that may be possessed by the aromatic ring represented by the following formula:

[0051] As the compound represented by formula (1), the compound represented by formula (4) is more preferred in that the effects of the present invention are more excellent.

[0052]

[0053] In formula (4), R ４１ and R ４２ R each independently represents a hydrogen atom or a substituent. ４３ ~R ４６ R each independently represents a hydrogen atom or a substituent. ａ４１ and R ａ４２ each independently represents an optionally substituted aryl group, —C(R Ｌ４１ ) (R Ｌ４２ ) (R Ｌ４３ ), or a heteroaryl group which may have a substituent. Ｌ４１ ~R Ｌ４３ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, provided that R Ｌ４１ ~R Ｌ４３ At least two of R represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Ｌ４１~R Ｌ４３ The optionally substituted alkyl group, the optionally substituted aryl group, and the optionally substituted heteroaryl group, represented by the following formula (I), may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. Examples of the divalent linking group include the groups exemplified above.

[0054] In formula (4), R ４１ and R ４２ The definition and preferred embodiments of the group represented by R in formula (1) １１ and R １２ is the same as the group represented by R ａ４１ and R ａ４２ The definition and preferred embodiments of the group represented by R in formula (1) ａ１１ and R ａ１２ In addition, -C(R Ｌ４１ ) (R Ｌ４２ ) (R Ｌ４３ ) and R Ｌ４１ ~R Ｌ４３ The definition and preferred embodiments of the group represented by -C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ) and R Ｌ１１ ~R Ｌ１３ is the same as the group represented by

[0055] In formula (4), R ４３ ~R ４６ Each independently represents a hydrogen atom or a substituent. Examples and preferred embodiments of the substituents are Ar in the above formula (1). １１ These are the same as the substituents that may be possessed by the aromatic ring represented by the following formula:

[0056] In formula (2), R ２１ and R ２２ R each independently represents a hydrogen atom or a substituent. ２１ and R ２２ Examples of the substituent represented by the formula (I) include the substituent W described above, and a hydrogen atom is preferred in terms of achieving better effects of the present invention.

[0057] In formula (2), R ２３ and R ２４each independently represents a substituent. Examples of the substituent include the substituent W described above. An optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group is preferred, with an optionally substituted alkyl group being more preferred. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6, in terms of achieving better quantum efficiency. The aryl group and heteroaryl group may be either monocyclic or polycyclic, with a monocyclic group being preferred. The heteroatom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. The number of ring atoms in the aryl group and heteroaryl group is preferably 5 to 12, more preferably 5 to 10. Examples of the substituent that the alkyl group, aryl group, and heteroaryl group may have include the substituent W described above. An alkyl group, an aryl group, a heteroaryl group, a cyano group, or a halogen atom is preferred, with an alkyl group or a halogen atom being more preferred.

[0058] R ２３ and R ２４ 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 ring, with an aliphatic ring being preferred. The ring may be either a monocyclic ring or a polycyclic ring. The number of ring atoms in the ring is preferably 3 to 20, more preferably 5 to 12, and even more preferably 5 to 10. The ring may have a heteroatom. 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, with a sulfur atom, a nitrogen atom, or an oxygen atom being preferred. Examples of the substituent which the ring may have include the substituent W described above, with an alkyl group, an aryl group, or a halogen atom being preferred.

[0059] In formula (2), R ａ２represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and an alkyl group which may have a substituent or an aryl group which may have a substituent is preferred in terms of obtaining better effects of the present invention.

[0060] R ａ２ The alkyl group represented by the formula (I) may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3, in terms of more excellent quantum efficiency. Examples of the substituent that the alkyl group may have include the substituent W, which is preferably an aryl group, a heteroaryl group, or a halogen atom.

[0061] R ａ２ The definitions and preferred embodiments of the optionally substituted aryl group and optionally substituted heteroaryl group represented by the formula (I) are as follows: ａ１１ and R ａ１２ The aryl group and heteroaryl group are the same as the optionally substituted aryl group and the optionally substituted heteroaryl group represented by the following formula:

[0062] In formula (2), Ar ２１represents an aromatic ring which may have a substituent. The aromatic ring may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred in terms of better effects of the present invention. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. Examples of heteroatoms contained in the aromatic heterocyclic ring are as described above, with an oxygen atom, a nitrogen atom, or a sulfur atom being preferred, and a nitrogen atom being more preferred. The number of ring atoms in the aromatic ring group is preferably 5 to 20, more preferably 5 to 10, and even more preferably 6. Examples of the substituent that the aromatic ring group may have include the substituent W described above, and preferred are a halogen atom, an optionally substituted aliphatic hydrocarbon group (preferably an alkyl group having 1 to 3 carbon atoms), an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group, an optionally substituted alkoxy group (preferably having 1 to 3 carbon atoms), an optionally substituted acyl group (preferably having 2 to 4 carbon atoms), an optionally substituted alkyloxycarbonyl group (preferably having 2 to 4 carbon atoms), a silyl group, a cyano group, or a nitro group, and preferred are a halogen atom, an optionally halogenated alkyl group (preferably having 1 to 3 carbon atoms), or an alkoxy group (preferably having 1 to 3 carbon atoms). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred, and a fluorine atom being more preferred.

[0063] In formula (2), C ２１represents a monocyclic ring having 5 or more ring atoms, which may have a substituent. The monocyclic ring has 5 or more ring atoms, preferably 5 or 6. Examples of the substituent that the monocyclic ring may have include the above-mentioned substituent W, and are preferably a halogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a silyl group, and more preferably a halogen atom or an alkyl group. The alkyl group may be linear, branched, or cyclic, and is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 3. The substituent that the alkyl may have is preferably a halogen atom, an aromatic ring group, or a silyl group. The substituent that the aromatic ring group may have is preferably a halogen atom, an alkyl group, or a silyl group. The above C ２１ Among the carbon atoms constituting the ring represented by ２２ or Z ２３ and a carbon atom bonded to R ２１ A carbon atom other than the carbon atom bonded to the carbon atom to which is bonded (in other words, a carbon atom other than the three carbon atoms explicitly shown in the formula) may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0064] In formula (2), Z ２１ and Z ２２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｙ１ , or =C(R Ｙ２ ) (R Ｙ３ ), and an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred, in that the effects of the present invention are more excellent. Ｙ１represents a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W, and an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent is preferred. The definition of the aliphatic hydrocarbon group is as described above, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferred. The definition of the aromatic ring group is as described above, and an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. The definition of the aliphatic heterocyclic group is as described above, and the heteroatom contained in the aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. R Ｙ１ Examples of the substituent that may be possessed by each group represented by the formula (I) include the substituents exemplified above for the substituent W. Ｙ２ and R Ｙ３ each independently represents a cyano group, —COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ Represents R Ｙ４ ~R Ｙ６ R each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Ｙ４ ~R Ｙ６ The definitions and preferred embodiments of each group represented by R Ｙ１ is the same as each group represented by

[0065] As the compound represented by formula (2), the compound represented by formula (5) is preferred in that the effects of the present invention are more excellent.

[0066]

[0067] In formula (5), R ５１ and R ５２ R each independently represents a hydrogen atom or a substituent. ５３ and R ５４ R each independently represents a substituent. ５３ and R ５４ may be bonded to each other to form a ring which may have a substituent. ａ５represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, provided that R ａ５ represents an alkyl group which may have a substituent, R ５３ and R ５４ each independently represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, or R ５１ and R ５２ are bonded to each other to form a ring which may have a substituent. ５５ ~R ５８ each independently represents a hydrogen atom or a substituent. ５１ represents a monocyclic ring having 5 or more ring atoms, which may have a substituent. ５１ and Z ５２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｙ１ , or =C(R Ｙ２ ) (R Ｙ３ ) represents. Ｙ１ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. Ｙ２ and R Ｙ３ each independently represents a cyano group, —COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ Represents R Ｙ４ ~R Ｙ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

[0068] In formula (5), R ５１ and R ５２ The definition and preferred embodiments of the group represented by R in formula (2) ２１ and R ２２ is the same as the group represented by R ５３ and R ５４ The definition and preferred embodiments of the group represented by R in formula (2) ２３ and R ２４ is the same as the group represented by Rａ５ The definition and preferred embodiments of the group represented by R in formula (2) ａ２ is the same as the group represented by ２１ The definition and preferred embodiment of the ring represented by the formula (2) are as follows: ５１ is the same as the ring represented by Z ５１ and Z ５２ The definition and preferred embodiments of the group represented by the formula (2) are ２１ and Z ２２ is the same as the group represented by the formula ａ５ represents an alkyl group which may have a substituent, R ５３ and R ５４ each independently represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, or R ５３ and R ５４ are bonded to each other to form a ring which may have a substituent. ａ５ represents an alkyl group which may have a substituent, R ５３ and R ５４ represents a group other than an alkyl group which may have a substituent, among the above groups. ５３ and R ５４ The details of the embodiment in which R are bonded to each other to form a ring which may have a substituent are as follows: ２３ and R ２４ are bonded to each other to form a ring which may have a substituent.

[0069] In formula (5), R ５５ ~R ５８ Each independently represents a hydrogen atom or a substituent. Examples and preferred embodiments of the substituents are Ar in the above formula (2). ２１ These are the same as the substituents that may be possessed by the aromatic ring represented by the following formula:

[0070] Specific examples of the first compound are shown below, but the present invention is not limited to these.

[0071]

[0072]

[0073]

[0074] The molecular weight of the first compound is preferably 400 to 750, more preferably 400 to 700, and even more preferably 400 to 650. When the molecular weight is within the above range, the sublimation temperature of the first compound is lowered, and it is presumed that the compound has excellent manufacturing suitability.

[0075] The first 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.

[0076] The first compound preferably has an absorption maximum wavelength in the wavelength range of 400 to 520 nm, and more preferably in the wavelength range of 400 to 500 nm. The absorption maximum wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the first compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the first compound is insoluble in chloroform, the absorption maximum wavelength of the first compound is determined by evaporating the first compound into a film state.

[0077] The first compound may be purified as necessary. Examples of methods for purifying the first compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.

[0078] The content of the first compound in the photoelectric conversion film (=film thickness of the first compound in terms of a single layer / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75% by volume, more preferably 5 to 50% by volume, and even more preferably 10 to 40% by volume. Only one type of first 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.

[0079] <Second Compound> The photoelectric conversion film contains a second compound which is a compound represented by formula (3).

[0080]

[0081] In formula (3), D３１ represents a group represented by formula (D-1) to formula (D-3), where n D ３１ At least one of the groups represented by formula (D-1) is a group represented by formula (D-1), and n is an integer of 1 to 3. When n is 2 or 3, a plurality of D ３１ may be the same or different from each other. ３１ and A ３２ each independently represents a group represented by formula (A-1) or formula (A-2). In formula (D-1), k represents an integer of 0 to 4. W １ａ and W ２ａ are each independently -Z ａ =Z ａ -C(*)=Z ａ - or -Z ａ = C(*)-X ａ - represents Y １ａ and Y ２ａ is one of the following combinations 1 to 4. Combination 1: Y １ａ and Y ２ａ are each independently -Z ａ = Combination 2: Y １ａ and Y ２ａ One of them is -Z ａ =Z ａ - and the other represents a single bond. １ａ and Y ２ａ One of them is -X ａ - and the other represents a single bond. １ａ and Y ２ａ One of the two is -C(T １ａ ) (T ２ａ )-Y ａ -, or -C(=X ｂ )-Y ａ - and the other represents a single bond. ａ are each independently -CR Ａ = or represents a nitrogen atom. Ａ represents a hydrogen atom or a substituent. ａ represents an oxygen atom, a sulfur atom, a selenium atom, -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２-, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ )-. Ａ１ ~R Ａ５ R each independently represents a hydrogen atom or a substituent. Ａ２ Comrade, R Ａ３ Comrade, R Ａ４ Peers and R Ａ５ and may be bonded to each other to form a ring which may have a substituent. １ａ and T ２ａ each independently represents a hydrogen atom or a substituent. ａ represents an oxygen atom, a sulfur atom, or —NR Ａ１ - represents X ｂ represents an oxygen atom or a sulfur atom. １ａ ~Z ６ａ Two of them represent -C(*)=, and four of them are each independently -CR Ａ In formula (D-3), Z represents a nitrogen atom. １１ａ ~Z １５ａ Two of them represent -C(*)=, and two of them are independently -CR Ａ = or a nitrogen atom, and one represents an oxygen atom, a sulfur atom, a selenium atom, or -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ In formula (A-1), C １ represents a ring containing two or more carbon atoms which may have a substituent. １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ１ , or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ represents a hydrogen atom or a substituent. Ｗ２ and R Ｗ３ each independently represents a cyano group, —COOR Ｗ４ , -COR Ｗ５ , or -SO ２ RＷ６ Represents R Ｗ４ ~R Ｗ６ 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. Ａ１ and R ａ２ each independently represents a cyano group, —COOR ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents R ｂ１ ~R ｂ４ 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. * represents a bonding position.

[0082] In formula (3), D ３１ represents a group represented by formula (D-1) to formula (D-3). The groups represented by formula (D-1) to formula (D-3) will be described later. n represents an integer of 1 to 3, and is preferably 1 or 2, more preferably 1, in terms of better effects of the present invention. n D ３１ At least one of the groups represented by formula (D-1) is a group represented by formula (D-1). ３１ represents a group represented by formula (D-1), and when n is 2 or 3, a plurality of D ３１ At least one of the groups represented by formula (D-1) is a group represented by formula (D-1). ３１ may be the same or different from each other.

[0083] In formula (3), A ３１ and A ３２ each independently represents a group represented by formula (A-1) or formula (A-2), and the group represented by formula (A-1) is preferred in that the effects of the present invention are more excellent. The group represented by formula (A-1) or formula (A-2) will be described later.

[0084] The groups represented by formulae (D-1) to (D-3) will be described in detail below.

[0085] In formula (D-1), k represents an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 1 or 2, in that the effects of the present invention are more excellent.

[0086] In formula (D-1), W １ａ and W ２ａ are each independently -Z ａ =Z ａ -C(*)=Z ａ - or -Z ａ = C(*)-X ａ - represents Z ａ are each independently -CR Ａ = or a nitrogen atom. Ａ represents a hydrogen atom or a substituent. Ａ Examples of the substituent represented by include the above-mentioned substituent W, and are preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an alkoxy group, an aryloxy group, an acyl group, a silyl group, a halogen atom, a cyano group, or a nitro group, and are more preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, a silyl group, an alkoxy group, or a halogen atom. Examples of the substituent which the aliphatic hydrocarbon group, aromatic ring group, and aliphatic heterocyclic group may have include the substituents exemplified for the above-mentioned substituent W, and are preferably a substituent selected from the substituent group S described below.

[0087] The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The linear aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 4, and particularly preferably 1 or 2. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 6.

[0088] The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic ring group may be either monocyclic or polycyclic, with a monocyclic group being preferred. The number of ring atoms in the aromatic ring group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 to 8. The definition and specific examples of the aromatic hydrocarbon group are as described above, with a phenyl group or naphthyl group being preferred, and a phenyl group being more preferred. Examples of heteroatoms contained in the aromatic heterocyclic group include sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. The definition and specific examples of the aromatic heterocyclic group are as described above, with a thiophene ring group, a furan ring group, or a pyridine ring group being preferred. The aromatic ring group may have a substituent, as described above. When the aromatic ring group has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 3.

[0089] The aliphatic heterocyclic group may be either monocyclic or polycyclic, with monocyclic being preferred. The number of ring atoms in the aliphatic heterocyclic group is preferably 3 to 18, more preferably 5 to 10, and even more preferably 5 to 8. Examples of heteroatoms contained in the aliphatic heterocyclic group include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen being preferred. The definition and specific examples of the aliphatic heterocyclic group are as described above, with a thiolane ring group, piperidine ring group, tetrahydrofuran ring group, or tetrahydropyran ring group being preferred. The aliphatic heterocyclic group may have a substituent, as described above. When the aliphatic heterocyclic group has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 3.

[0090] The alkyl group of the alkoxy group may be linear, branched, or cyclic. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

[0091] The aryl group in the aryloxy group may be either monocyclic or polycyclic, preferably monocyclic, and preferably has 5 to 18 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.

[0092] The hydrocarbon group contained in the acyl group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred. A preferred embodiment of the aliphatic hydrocarbon group and aromatic hydrocarbon group contained in the acyl group is R Ａ The acyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms.

[0093] The silyl group is —SiR Ｓｉ ３ R is a group represented by the formula: Ｓｉ 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. Ｓｉ The definitions and preferred embodiments of the optionally substituted aliphatic hydrocarbon group, the optionally substituted aromatic ring group, and the optionally substituted aliphatic heterocyclic group represented by the formula (I) are as follows: Ａ is the same as each of the groups exemplified as the substituent represented by the formula:

[0094] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred.

[0095] X ａ represents an oxygen atom, a sulfur atom, a selenium atom, -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ )-, an oxygen atom, a sulfur atom, -NR Ａ１ -, -SiR Ａ２ ２ - or -CR Ａ４ ２- is preferred. Ａ１ ~R Ａ５ R each independently represents a hydrogen atom or a substituent. Ａ１ ~R Ａ５ Examples of the substituent represented by R include the substituents exemplified for the substituent W described above, and an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group is preferred, an optionally substituted aliphatic hydrocarbon group or an optionally substituted aromatic ring group is more preferred, and an optionally substituted aliphatic hydrocarbon group is even more preferred. Ａ１ ~R Ａ５ The definitions and preferred embodiments of each group exemplified as the substituent represented by R Ａ is the same as each of the groups exemplified as the substituent represented by the formula:

[0096] R Ａ２ Comrade, R Ａ３ Comrade, R Ａ４ Peers and R Ａ５ may be bonded to each other to form a ring which may have a substituent. Ａ２ may be bonded to each other to form a ring which may have a substituent, and R Ａ３ may be bonded to each other to form a ring which may have a substituent, and R Ａ４ may be bonded to each other to form a ring which may have a substituent, and R Ａ５ They 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 ring, with an aliphatic ring being preferred. The ring may be either a monocyclic ring or a polycyclic ring. The number of ring members in the ring is preferably 3 to 20, more preferably 5 to 12, and even more preferably 5 to 10. The ring may have a heteroatom. The heteroatom is preferably a sulfur atom, a nitrogen atom, or an oxygen atom. Examples of the substituent which the ring may have include the substituent W described above, with an alkyl group, an aryl group, or a halogen atom being preferred.

[0097] In formula (D-1), Y １ａ and Y ２ａis one of the following combinations 1 to 4. Combination 1: Y １ａ and Y ２ａ are each independently -Z ａ = Combination 2: Y １ａ and Y ２ａ One of them is -Z ａ =Z ａ - and the other represents a single bond. １ａ and Y ２ａ One of them is -X ａ - and the other represents a single bond. １ａ and Y ２ａ One of the two is -C(T １ａ ) (T ２ａ )-Y ａ -, or -C(=X ｂ )-Y ａ -, and the other represents a single bond.

[0098] T １ａ and T ２ａ Each independently represents a hydrogen atom or a substituent. The definition and preferred embodiments of the above substituents are the same as those of R Ａ１ ~R Ａ５ is the same as the substituent represented by Y ａ represents an oxygen atom, a sulfur atom, or —NR Ａ１ - represents. Ａ１ is as described above. ｂ represents an oxygen atom or a sulfur atom.

[0099] Examples of the group represented by formula (D-1) include groups represented by formula (D-11).

[0100]

[0101] In formula (D-11), A and C each independently represent a ring represented by formula (d1) or formula (d2). B each independently represent a ring represented by any one of formulas (d3) to (d7). k represents an integer of 0 to 4. In formulas (d1) to (d7), Z ａ , X ａ , T １ａ , T ２ａ , Y ａ , and X ｂThe definition and preferred embodiments of Z in formula (D-1) are as follows: ａ , X ａ , T １ａ , T ２ａ , Y ａ , and X ｂ is the same as above. * represents a bonding position. The rings represented by the formula (d1) and the formula (d2) are fused at the fused ring positions represented by two *1. The rings represented by the formulas (d3) to (d7) are fused to one adjacent ring at the fused ring positions represented by two *2, and are fused to the other adjacent ring at the fused ring positions represented by two *3.

[0102] In formula (D-2), Z １ａ ~Z ６ａ Two of them represent -C(*)=, and four of them are each independently -CR Ａ = or a nitrogen atom. １ａ ~Z ６ａ Two of them represent -C(*)= and four represent -CR Ａ It is preferred that R represents ≡ Ａ is as described above in formula (D-1). * represents a bonding position.

[0103] In formula (D-3), Z １１ａ ~Z １５ａ Two of them represent -C(*)=, and two of them are independently -CR Ａ = or a nitrogen atom, and one represents an oxygen atom, a sulfur atom, a selenium atom, or -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ )-. Among them, Z １１ａ ~Z １５ａ Two of them are -CR Ａ In addition, Z is preferably １１ａ ~Z １５ａ one of which is an oxygen atom, a sulfur atom, or —NR Ａ１ - is preferred, and an oxygen atom or a sulfur atom is more preferred. Ａ and R Ａ１ ~RＡ５ is as described above in formula (D-1). Ａ２ Comrade, R Ａ３ Comrade, R Ａ４ Peers and R Ａ５ may be bonded to each other to form a ring which may have a substituent. Details of the ring which may have a substituent are as described above in formula (D-1). * represents the bonding position.

[0104] As the group represented by formula (D-1), groups represented by formulas (B1) to (B31) are preferred, and groups represented by formulas (B5) to (B29) are more preferred. As the group represented by formula (D-2), groups represented by formulas (A1) to (A3) are preferred. As the group represented by formula (D-3), groups represented by formula (A4) are preferred. * indicates a bonding position.

[0105]

[0106]

[0107]

[0108] In the above formulas (A1) to (A4) and (B1) to (B31), each Z is independently -CR Ａ = or a nitrogen atom, -CR Ａ X and X are preferred. Ｉ each independently represents an oxygen atom, a sulfur atom, a selenium atom, or —NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ X represents an oxygen atom, a sulfur atom, or —NR Ａ１ - is preferred, and an oxygen atom or a sulfur atom is more preferred. Ｉ As the electrons, oxygen atoms, sulfur atoms, selenium atoms, -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３２ - or -CR Ａ４ ２ - is preferred, and an oxygen atom, a sulfur atom, a selenium atom, or -NR Ａ１ -, -SiR Ａ２ ２ - or -CR Ａ４ ２ - is more preferred, and an oxygen atom, a sulfur atom, or -CR Ａ４ ２ Each Y is independently an oxygen atom, a sulfur atom, or —NR Ａ１ -, and an oxygen atom or a sulfur atom is preferred. Ａ and R Ａ１ ~R Ａ５ is as described above. Ａ２ Comrade, R Ａ３ Comrade, R Ａ４ Peers and R Ａ５ and may be bonded to each other to form a ring which may have a substituent. Details of the ring which may have a substituent are as described above in formula (D-1). １ and T ２ each independently represents a hydrogen atom or a substituent. １ and T ２ The definition and preferred embodiments of T １ａ and T ２ａ is the same as

[0109] In formula (A-1), C １ represents a ring containing two or more carbon atoms and which may have a substituent. １The two carbon atoms contained in are the two carbon atoms specified in formula (A-1). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the two carbon atoms specified in the formula. The ring may be either an aromatic ring or an aliphatic ring. The ring may be either a monocyclic or polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms in the ring is preferably 0 to 10, and more preferably 0 to 5. １ Among the carbon atoms constituting the ring represented by the formula (A-1), the carbon atom at the bonding position marked with * and W １ Carbon atoms other than the carbon atom bonded to may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0110] Examples of the substituent that the ring may have include the groups exemplified for the substituent W above, and are preferably a halogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a silyl group, and more preferably a halogen atom or an alkyl group. The alkyl group may be linear, branched, or cyclic, and is preferably linear. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms. The substituent that the alkyl may have is preferably a halogen atom, an aromatic ring group, or a silyl group. The substituent that the aromatic ring group may have is preferably a halogen atom, an alkyl group, or a silyl group.

[0111] The ring represented by formula (A-1) is preferably a ring used as an acidic nucleus (for example, an acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, a 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione; (b) pyrazolinone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one; (c) isoxazolinone nucleus: for example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one; (d) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole. (e) 2,4,6-trioxohexahydropyrimidine nucleus: For example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl, and 1,3-dibutyl, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl), and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl). (f) 2-thio-2,4-thiazolidinedione nucleus: For example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-heteroarylrhodanines such as 3-(2-pyridyl)rhodanine. (g) 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazoledione nucleus): for example, 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone nucleus: for example, 3(2H)-thianaphthenone-1,1-dioxide. (i) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione.(j) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione. (k) thiazolin-4-one nucleus: for example, 4-thiazolinone and 2-ethyl-4-thiazolinone. (l) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione. (n) Imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one, etc. (o) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione, etc. (p) Benzothiophen-3(2H)-one nucleus: for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one, etc. (q) Indanone nucleus: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone, etc. (r) Benzofuran-3-(2H)-one nucleus: for example, benzofuran-3-(2H)-one, etc. (s) 2,2-dihydrophenalene-1,3-dione nucleus, etc.

[0112] W １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of achieving better effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ represents a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent W. In a preferred embodiment, R Ｙ１ is the same as the group represented by R Ｗ２ and R Ｗ３ each independently represents a cyano group, —COOR Ｗ４ , -COR Ｗ５ , or -SO２ R Ｗ６ Represents R Ｗ４ ~R Ｗ６ 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 4 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 a sulfur atom, an oxygen atom, or a nitrogen atom. R Ｗ４ ~R Ｗ６ Examples of the substituent that each group represented by the following formula may have include the substituent W described above.

[0113] As the group represented by formula (A-1), a group represented by formula (A-3) is preferred in that the effects of the present invention are more excellent.

[0114]

[0115] In formula (A-3), C ２ represents a ring containing at least three carbon atoms, which may have a substituent. ２ The three carbon atoms contained in are the three carbon atoms specified in formula (A-3). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the three carbon atoms specified in the formula. The ring may be either an aromatic ring or an aliphatic ring. The ring may be either a monocyclic or polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5.２ Among the carbon atoms constituting the ring represented by the formula (A-2), the carbon atom at the bonding position marked with * and W ２ Or W ３ A carbon atom other than the carbon atom bonded to the ring C may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S). １ The substituents are the same as those that may be possessed by the group.

[0116] In formula (A-3), W ２ and W ３ are each independently a sulfur atom, an oxygen atom, or ═NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of achieving better effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ ~R Ｗ３ is as described above.

[0117] The group represented by formula (A-3) is more preferably a group represented by formula (C-1) or a group represented by formula (C-2).

[0118]

[0119] In formula (C-1), X ｃ１ and X ｃ２ Each of X independently represents an oxygen atom or a sulfur atom. ｃ１ and X ｃ２ is preferably an oxygen atom, and X ｃ１ and X ｃ２ is more preferably an oxygen atom.

[0120] In formula (C-1), C ３represents an aromatic ring which may have a substituent. The aromatic ring may be either a monocyclic or polycyclic ring. The number of ring-member atoms of the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of ring-member atoms of the aromatic ring is the number including the two carbon atoms specified in the formula. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. Specific examples of the aromatic ring are as described above, with a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyridine ring, a thienothiophene ring, a benzothiophene ring, a benzofuran ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring being preferred, a benzene ring, a naphthalene ring, or a thiophene ring being more preferred, and a benzene ring being even more preferred. Examples of the substituent which the aromatic ring may have include the groups exemplified by the substituent W above, with an alkyl group or a halogen atom being preferred. The number of substituents that the aromatic ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.

[0121] In formula (C-2), X ｃ３ ~X ｃ５ Each of X independently represents an oxygen atom or a sulfur atom. ｃ３ and X ｃ４ is preferably an oxygen atom, and X ｃ３ ~X ｃ５ is more preferably an oxygen atom.

[0122] In formula (C-2), Z ａ１ and Z ａ２ are each independently -NR ｃ１ -or-CR ｃ２ R ｃ３ -, and the effect of the present invention is more excellent, -NR ｃ１ - is preferred. ｃ１ ~R ｃ３each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified by the substituent W above, with an alkyl group or an aryl group being preferred, and an alkyl group being more preferred. The alkyl group may be linear, branched, or cyclic, with a linear group being preferred. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The aryl group may be monocyclic or polycyclic, with a phenyl group being preferred. The aryl group may further have a substituent, and examples of the substituent include the groups exemplified by the substituent W above.

[0123] In formula (A-2), R Ａ１ and R Ａ２ each independently represents a cyano group, —COOR ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents R ｂ１ ~R ｂ４ 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. ｂ１ ~R ｂ４ The definitions and preferred embodiments of each group represented by R Ｗ４ ~R Ｗ６ is the same as the group represented by R ｂ１ ~R ｂ４ Among these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a phenyl group is preferred.

[0124] Substituent group S will be described in detail. Substituent group S: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 7 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, aromatic ring groups having 5 to 12 ring atoms which may have a substituent, alkoxy groups having 1 to 5 carbon atoms, acyl groups having 2 to 6 carbon atoms, silyl groups, and halogen atoms.

[0125] The number of carbon atoms in the linear aliphatic hydrocarbon group in the above-mentioned substituent group S is 1 to 3, and more preferably 1 or 2. The number of carbon atoms in the branched aliphatic hydrocarbon group in the above-mentioned substituent group S is 3 to 7, and more preferably 3 or 4. The cyclic aliphatic hydrocarbon group in the above-mentioned substituent group S is preferably monocyclic.

[0126] The aromatic ring group in the substituent group S may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The heteroatom contained in the aromatic heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The number of ring atoms in the aromatic ring group is 5 to 12, preferably 5 to 10, and more preferably 5 or 6. Examples of the substituent that the aromatic ring group may have include the substituents exemplified for the substituent W described above. A substituent selected from the substituent group S is preferred, and a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 7 carbon atoms, a silyl group, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom is more preferred. When the aromatic ring group has a substituent, the number of substituents is preferably 1 to 3.

[0127] The number of carbon atoms in the alkoxy group in the above-mentioned Substituent Group S is 1 to 5, more preferably 1 to 4, and still more preferably 1 or 2. The number of carbon atoms in the acyl group in the above-mentioned Substituent Group S is 2 to 6, preferably 2 to 5, and still more preferably 2 or 3.

[0128] The definition and preferred embodiments of the silyl group in the above-mentioned substituent group S are the same as those of the above-mentioned R Ａ Among them, the silyl group represented by R Ｓｉ are each independently a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 7 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group having 5 to 12 ring atoms which may have a substituent; Ｓｉ ３ A group represented by the following formula is preferred.

[0129] Examples of the halogen atom in the above-mentioned substituent group S include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0130] Specific examples of the second compound are shown below, but the present invention is not limited to these. In the following, Me represents a methyl group, and TMS represents a trimethylsilyl group.

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] In the compounds exemplified above, each A independently represents one of the following groups: Two A's may be the same or different.

[0146]

[0147]

[0148]

[0149]

[0150] The molecular weight of the second compound is preferably 400 to 900, more preferably 400 to 800, and even more preferably 400 to 700. When the molecular weight is within the above range, the sublimation temperature of the second compound is lowered, and it is presumed that the compound has excellent manufacturing suitability.

[0151] The second 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.

[0152] The second compound preferably has a maximum absorption wavelength in the wavelength range of 500 to 700 nm, more preferably in the wavelength range of 500 to 650 nm. The method for measuring the maximum absorption wavelength is the same as the method for measuring the maximum absorption wavelength of the first compound.

[0153] The second compound may be purified as needed. Examples of methods for purifying the second compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.

[0154] The content of the second compound in the photoelectric conversion film (=film thickness of specific compound in terms of a single layer / film thickness of photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75% by volume, more preferably 5 to 50% by volume, and even more preferably 10 to 40% by volume. Only one type of second 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.

[0155] It is also preferable that the first compound does not contain the following compound 1.

[0156]

[0157] In the photoelectric conversion film, the content of the first compound relative to the content of the second compound (film thickness of the first compound in monolayer equivalent / film thickness of the second compound in monolayer equivalent×100) is preferably 40 to 240% by volume, more preferably 40 to 180% by volume, and even more preferably 40 to 150% by volume. In the photoelectric conversion film, the total content of the first compound and the second compound ((film thickness of the first compound in monolayer equivalent+film thickness of the second compound in monolayer equivalent) / film thickness of the photoelectric conversion film×100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 20 to 50% by volume.

[0158] The photoelectric conversion film containing the first compound and the second 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.

[0159] The configuration of the photoelectric conversion film of each embodiment will be described in detail below.

[0160] <<Photoelectric Conversion Film of First Aspect>> The photoelectric conversion film of the first aspect has a mixed layer formed in a state in which a first compound and a second compound are mixed. Details of the first compound and the second compound are as described above. The photoelectric conversion film of the first aspect is preferably a layer made of the mixed layer.

[0161] <n-Type Organic Semiconductor> The photoelectric conversion film of the first embodiment preferably further contains an n-type organic semiconductor, and more preferably the mixed layer contains an n-type organic semiconductor. The n-type organic semiconductor is a compound different from the first compound and the second 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 carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one 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 dianhydride; 1,4,5,8-naphthalenetetracarboxylic 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 dianhydride; 3,4,9,10-perylenetetracarboxylic diimide derivatives; and the compounds described in paragraphs

[0056] to

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

[0162] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred. For example, fullerene C６０ , fullerene C ７０ , fullerene C ７６ , fullerene C ７８ , fullerene C ８０ , fullerene C ８２ , fullerene C ８４ , fullerene C ９０ , fullerene C ９６ , fullerene C ２４０ , fullerene C ５４０ 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.

[0163] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0164] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less or in the range of 500 to 600 nm.

[0165] When the mixed layer contains an n-type organic semiconductor, the mixed layer preferably has a bulk heterostructure formed by mixing the first compound, the second compound, and the n-type organic semiconductor. The bulk heterostructure is a layer in which the first compound, the second compound, and the n-type organic semiconductor are mixed and dispersed within the photoelectric conversion film. 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.

[0166] The difference in electron affinity between the first compound and the n-type organic semiconductor is preferably 0.1 eV or more.The difference in electron affinity between the second compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0167] When the photoelectric conversion film of the first embodiment 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%.

[0168] 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.

[0169] When the photoelectric conversion film of the first embodiment contains an n-type organic semiconductor, in terms of the response speed of the photoelectric conversion element, the total content of the first compound and the second compound relative to the total content of the first compound, the second compound, and the n-type organic semiconductor ((film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the second compound) / (film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the second compound + film thickness in monolayer equivalent of the n-type organic semiconductor)×100) is preferably 20 to 80 vol %, more preferably 40 to 80 vol %. When the photoelectric conversion film of the first embodiment contains an n-type organic semiconductor and a p-type organic semiconductor described later, the total content of the first compound and the second compound ((thickness of the first compound in monolayer equivalent + thickness of the second compound in monolayer equivalent) / (thickness of the first compound in monolayer equivalent + thickness of the second compound in monolayer equivalent + thickness of the n-type organic semiconductor in monolayer equivalent + thickness of the p-type organic semiconductor in monolayer equivalent) × 100) is preferably 10 to 75 vol%, more preferably 15 to 50 vol%. It is preferable that the mixed layer is substantially composed of the first compound, the second compound, the n-type organic semiconductor, and a p-type organic semiconductor that is included as desired. The term "substantially" means that the total content of the first compound, the second compound, the n-type organic semiconductor, and the p-type organic semiconductor relative to the total volume of the mixed layer is 90 to 100 vol%, preferably 95 to 100 vol%, more preferably 99 to 100 vol%.

[0170] <P-type organic semiconductor> The photoelectric conversion film of the first embodiment preferably further contains a p-type organic semiconductor, and more preferably the mixed layer contains a p-type organic semiconductor. The p-type organic semiconductor is a compound different from the first compound and the second 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 with the 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.

[0171] 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] Benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of JP2018-014474A, compounds described in paragraphs

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

[0034] of JP2017-076766A, compounds described in paragraphs

[0015] to

[0025] of WO2018 / 207722A, and compounds described in paragraph [00 45] to

[0053] , compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

[0036] of JP2019-80052A, 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,Compounds described in paragraphs

[0033] to

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

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

[0019] to

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

[0031] to

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

[0036] to

[0041] of JP-A No. 2018-166200 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, and paragraphs of JP-A No. 2018-014474

[0031] to

[0036] compounds described in paragraphs

[0036] to

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

[0045] to

[0048] of JP-A-2020-010024, 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. Examples of p-type organic semiconductors include benzoxazole compounds (for example, compounds described in Figures 3 to 7 of JP-A-2022-123944), dicarbazole compounds (for example, compounds described in Figures 2 to 5 of JP-A-2022-122839), benzoquinazoline compounds (for example, compounds described in paragraphs

[0053] to

[0056] of JP-A-2022-120323),Azine compounds (for example, compounds described in paragraphs

[0041] to

[0042] of JP-A No. 2022-120273), compounds described in Figures 2 to 10 of JP-A No. 2022-115832, indolotriphenylene compounds (for example, compounds described in paragraphs

[0065] to

[0072] of JP-A No. 2022-108268), indolocarbazole compounds (for example, compounds described in paragraphs

[0052] to [00 73] and the compounds described in paragraph

[0028] of JP-A No. 2022-100258), triscarbazolylphenyl compounds (for example, the compounds described in paragraphs

[0038] to

[0040] of JP-A No. 2022-181226), the compounds described in paragraphs

[0070] to

[0082] of JP-A No. 2022-027575, and the compounds described in paragraphs

[0051] to

[0064] of JP-A No. 2021-163968. Examples of p-type organic semiconductors include compounds having 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.

[0172]

[0173]

[0174]

[0175]

[0176] When the mixed layer contains an n-type organic semiconductor and a p-type organic semiconductor, it preferably has a bulk heterostructure formed in a state where the first compound, the second compound, the n-type organic semiconductor, and the p-type organic semiconductor are mixed.

[0177] The difference in ionization potential between the first compound and the p-type organic semiconductor is preferably 0.1 eV or more, and the difference in ionization potential between the second compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0178] When the photoelectric conversion film of the first embodiment 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%.

[0179] <Film formation method> Examples of the film formation method for the photoelectric conversion film of the first embodiment include a dry film formation method. For example, a mixed layer can be formed by forming a film by a dry film formation method using the first compound, the second compound, and, if necessary, an n-type organic semiconductor and a p-type organic semiconductor as raw materials. 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, with vacuum deposition being preferred. When forming a photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0180] The thickness of the photoelectric conversion film of the first embodiment is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm. The thickness of the mixed layer is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm. The total thickness of the mixed layer relative to the thickness of the photoelectric conversion film of the first embodiment is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. The upper limit is 100%, and 100% is preferred.

[0181] <<Photoelectric Conversion Film of Second Aspect>> The photoelectric conversion film of the second aspect has a first layer containing a first compound and a second layer containing a second compound. Details of the first compound and the second compound are as described above. The stacking order of the first layer and the second layer is not particularly limited. For example, the photoelectric conversion element may be stacked in the order of a conductive film, the first layer, the second layer, and a transparent conductive film, or may be stacked in the order of a conductive film, the second layer, the first layer, and a transparent conductive film. The photoelectric conversion film of the first aspect is preferably a layer consisting of the first layer and the second layer. Furthermore, it is preferable that the first layer and the second layer are directly stacked.

[0182] The content of the first compound in the first layer (=film thickness of the first compound in terms of a single layer / film thickness of the first layer × 100) is not particularly limited, but is preferably 10 to 75 vol%, more preferably 15 to 50 vol%. The content of the second compound in the second layer (=film thickness of the second compound in terms of a single layer / film thickness of the second layer × 100) is not particularly limited, but is preferably 10 to 75 vol%, more preferably 15 to 50 vol%.

[0183] <n-Type Organic Semiconductor> The photoelectric conversion film of the second embodiment preferably further contains an n-type organic semiconductor, and more preferably the first layer and the second layer further contain an n-type organic semiconductor. The definition and preferred embodiments of the n-type organic semiconductor in the photoelectric conversion film of the second embodiment are the same as those of the n-type organic semiconductor in the photoelectric conversion film of the first embodiment.

[0184] When the first layer contains an n-type organic semiconductor, it preferably has a bulk heterostructure formed by mixing the first compound and the n-type organic semiconductor.When the second layer contains an n-type organic semiconductor, it preferably has a bulk heterostructure formed by mixing the second compound and the n-type organic semiconductor.

[0185] When the photoelectric conversion film of the second embodiment 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 monolayer equivalent / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and even more preferably 20 to 50 vol%. When the first layer contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the first layer (thickness of the n-type organic semiconductor in monolayer equivalent / thickness of the first layer × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and even more preferably 20 to 50 vol%. When the second layer contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the second layer (thickness of the n-type organic semiconductor in monolayer equivalent / thickness of the second layer × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and even more preferably 20 to 50 vol%.

[0186] When the photoelectric conversion film of the second embodiment contains an n-type organic semiconductor, in terms of the response speed of the photoelectric conversion element, the total content of the first compound and the second compound relative to the total content of the first compound, the second compound, and the n-type organic semiconductor ((film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the second compound) / (film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the second compound + film thickness in monolayer equivalent of the n-type organic semiconductor) × 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume. In the first layer, the content of the first compound relative to the total content of the first compound and the n-type organic semiconductor (film thickness in monolayer equivalent of the first compound / (film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the n-type organic semiconductor) × 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume. In the second layer, the content of the second compound relative to the total content of the second compound and the n-type organic semiconductor (thickness of the second compound in terms of a single layer / (thickness of the second compound in terms of a single layer+thickness of the n-type organic semiconductor in terms of a single layer)×100) is preferably 20 to 80 vol %, and more preferably 40 to 80 vol %.

[0187] When the photoelectric conversion film of the second embodiment contains an n-type organic semiconductor and a p-type organic semiconductor, the total content of the first compound and the second compound ((film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the second compound) / (film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the second compound + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the p-type organic semiconductor) × 100) is preferably 10 to 75 vol%, more preferably 15 to 50 vol%. When the first layer contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the first compound ((film thickness in monolayer equivalent of the first compound) / (film thickness in monolayer equivalent of the first compound + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the p-type organic semiconductor) × 100) is preferably 10 to 75 vol%, more preferably 15 to 50 vol%. When the second layer contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the second compound (film thickness of the second compound in terms of a single layer / (film thickness of the second compound in terms of a single layer+film thickness of the n-type organic semiconductor in terms of a single layer+film thickness of the p-type organic semiconductor in terms of a single layer)×100) is preferably 10 to 75 vol%, more preferably 15 to 50 vol%.

[0188] It is preferable that the first layer be substantially composed of a first compound, an n-type organic semiconductor, and an optionally included p-type organic semiconductor. "Substantially" means that the total content of the first compound, n-type organic semiconductor, and p-type organic semiconductor is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume, relative to the total volume of the photoelectric conversion film. The second layer is preferably substantially composed of a second compound, an n-type organic semiconductor, and an optionally included p-type organic semiconductor. "Substantially" means that the total content of the second compound, n-type organic semiconductor, and p-type organic semiconductor is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume, relative to the total volume of the photoelectric conversion film.

[0189] <p-type organic semiconductor> The photoelectric conversion film of the second embodiment preferably further contains a p-type organic semiconductor, and more preferably the first layer and the second layer further contain a p-type organic semiconductor. The definition and preferred embodiments of the p-type organic semiconductor in the photoelectric conversion film of the second embodiment are the same as those of the p-type organic semiconductor in the photoelectric conversion film of the first embodiment.

[0190] When the first layer contains a p-type organic semiconductor, it preferably has a bulk heterostructure formed by mixing the first compound, an n-type organic semiconductor, and a p-type organic semiconductor.When the second layer contains an n-type organic semiconductor, it preferably has a bulk heterostructure formed by mixing the second compound, an n-type organic semiconductor, and a p-type organic semiconductor.

[0191] When the photoelectric conversion film of the second embodiment 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 even more preferably 25 to 50 vol%. When the first layer contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the first layer (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 even more preferably 25 to 50 vol%. When the second layer contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the second layer (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 even more preferably 25 to 50 vol%.

[0192] <Film formation method> Examples of the film formation method for the photoelectric conversion film of the second embodiment include a dry film formation method. For example, a first film (first layer) is formed by a dry film formation method using a first compound and, if necessary, an n-type organic semiconductor and a p-type organic semiconductor as raw materials, and then a second film (second layer) is formed on the first film by a dry film formation method using a second compound and, if necessary, an n-type organic semiconductor and a p-type organic semiconductor as raw materials, thereby forming a photoelectric conversion film. Examples of the dry film formation method include the dry film formation methods exemplified as the film formation method for the photoelectric conversion film of the first embodiment, and the same applies to preferred embodiments.

[0193] The film thickness of the photoelectric conversion film is preferably 10 to 1,000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm. The film thickness of the first layer is preferably 5 to 500 nm, more preferably 25 to 400 nm, and even more preferably 25 to 250 nm. The film thickness of the second layer is preferably 5 to 500 nm, more preferably 25 to 400 nm, and even more preferably 25 to 250 nm. The ratio of the thickness of the first layer to the film thickness of the photoelectric conversion film is preferably 30 to 70%, and more preferably 40 to 60%. The ratio of the thickness of the second layer to the film thickness of the photoelectric conversion film is preferably 30 to 70%, and more preferably 40 to 60%. The ratio of the total film thickness of the first and second layers to the film thickness of the photoelectric conversion film is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. The upper limit is 100%, and 100% is preferred.

[0194] [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); metal thin 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.

[0195] 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 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.

[0196] 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, 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 graphene.

[0197] 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.

[0198] [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.

[0199] <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, and diacetylene, as well as derivatives thereof.

[0200] 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.

[0201] <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.

[0202] Examples of methods for producing a charge blocking film include dry film formation and wet film formation. Examples of dry film formation methods 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 methods 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.

[0203] 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.

[0204] [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.

[0205] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. The performance of photoelectric conversion materials may be significantly degraded in the presence of degrading factors such as water molecules. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of a ceramic such as a dense metal oxide, metal nitride, or metal nitride oxide, or diamond-like carbon (DLC), which does not allow water molecules to penetrate. Examples of the sealing layer include the sealing layers described in paragraphs

[0210] to

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

[0206] [Method for manufacturing photoelectric conversion element] Examples of methods for manufacturing photoelectric conversion elements include known manufacturing methods. Specifically, for example, methods for manufacturing photoelectric conversion elements include a step of forming a conductive film on a substrate, a step of forming a photoelectric conversion film, and a step of forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer) in addition to the above. The method for forming each layer is as described above.

[0207] [Imaging element] An example of an application of a photoelectric conversion element is an imaging element. An imaging element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal and outputting the electrical signal pixel by pixel from the imaging element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The manufacturing method of an imaging element is not particularly limited, but examples include a method including the step of manufacturing the photoelectric conversion element described above.

[0208] [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.

[0209] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, 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 examples shown below.

[0210] [Compounds used in photoelectric conversion film] The materials used in the photoelectric conversion film are shown below.

[0211] [First Compound] The first compounds used in the photoelectric conversion film and a comparative compound (comparative compound 1) for the comparative example are shown below. Compounds B-1 to B-13 are first compounds, and compounds C-1 and C-2 are comparative compound 1.

[0212]

[0213] [Second Compound] The second compounds used in the photoelectric conversion film and a comparative compound (comparative compound 2) for comparison are shown below. Compounds R-1 to R-14 are second compounds, and compound C-3 is comparative compound 2. In the following, k and n represent n in formula (3) and k in the group represented by formula (D-1). For example, compound R-8 has n=2 in formula (3), and one D ３１ is a group represented by formula (D-1) in which k=1.

[0214]

[0215] [n-type organic semiconductor] C60: fullerene (C ６０ )

[0216] [p-type organic semiconductor]

[0217]

[0218] [Synthesis of First Compound and Second Compound] [Synthesis of Compound B-1] Compound B-1 was synthesized according to the following scheme.

[0219]

[0220] <Synthesis of Compound (B-1-1)> To a mixture of 2,3-dichloroquinoxaline (20.0 g, 100 mmol), 2,6-diisopropylaniline (42 mL, 220 mmol), and tetrahydrofuran (100 mL), a 35% by mass solution of sodium hexamethyldisilazane in tetrahydrofuran (1.9 mol / L) (237 mL, 450 mmol) was added dropwise. The mixture was stirred at 60°C for 1 hour and then allowed to cool to room temperature. Water (200 mL) was added dropwise to the mixture. 100 mL of 20% by mass brine was then added to the mixture, and the organic layer of the mixture was extracted. The resulting organic layer was dried over magnesium sulfate and then filtered. The filtrate was concentrated under reduced pressure. The crude product obtained after concentration under reduced pressure was dispersed in 2-propanol and washed. The washed crude product was filtered, and the filter cake was dried under reduced pressure to obtain compound (B-1-1) (33.7 g, yield 70%).

[0221] <Synthesis of Compound (B-1-2)> p-Toluenesulfonic acid monohydrate (35.6 g, 187 mmol), acetic anhydride (62 mL), and compound (B-1-1) (30.0 g, 62.4 mmol) were mixed, and the resulting reaction solution was stirred at 130°C for 3 hours. The reaction solution was allowed to cool to room temperature and added dropwise to a mixture of 50 w / v% aqueous sodium hydroxide (100 mL) and ice (440 g), and the resulting reaction mixture was stirred for 30 minutes. Acetic acid was added to the reaction mixture to adjust the pH to 8 at 25°C, and the reaction mixture was further stirred for 20 minutes. The resulting precipitate was filtered, and the resulting crude product (filtered product) was washed with water and then methanol. The washed crude product was reprecipitated using dichloromethane / methanol. The target product obtained by reprecipitation was filtered off, and the target product (filtered product) was dried under reduced pressure to obtain compound (B-1-2) (26.8 g, yield 87%).

[0222] <Synthesis of Compound (B-1-3)> Compound (B-1-2) (25.0 g, 49.5 mmol) was added to a mixture of (chloromethylene)dimethyliminium chloride (15.8 g, 124 mmol) and acetonitrile (100 mL), and the resulting reaction solution was stirred at 60°C for 2 hours. The reaction solution was allowed to cool to room temperature and added dropwise to a mixture of 1 mol / L aqueous sodium hydroxide solution (375 mL) and ice (250 g), and the resulting mixture was stirred for 1 hour. The precipitate formed in the mixture was filtered, and the resulting crude product (filtered product) was washed with water and then methanol. The washed crude product was reprecipitated using dichloromethane / acetonitrile. The target product obtained by reprecipitation was collected by filtration, and the target product (filtered product) was dried under reduced pressure to obtain compound (B-1-3) (16.4 g, yield 62%).

[0223] <Synthesis of Compound B-1> Malononitrile (2.84 mL, 45.1 mmol) was added to a mixture of compound (B-1-3) (12.0 g, 22.5 mmol), sodium acetate (3.70 g, 45.1 mmol), and n-butanol (120 mL), and the resulting reaction solution was stirred at 120°C for 8 hours. The mixture was allowed to cool to room temperature, and the resulting precipitate was filtered. The resulting crude product (filtered product) was washed with methanol. The washed crude product was reprecipitated using dichloromethane / methanol. The target product obtained by reprecipitation was collected by filtration, and the target product (filtered product) was purified by sublimation to obtain (B-1) (8.3 g, 64%).

[0224] The resulting compound B-1 was identified by NMR (Nuclear Magnetic Resonance), and the results are as follows. １ H-NMR (CDCl ３ , 400MHz) δ = 7.90-7.95 (2H, m), 7.73 (1H, t), 7.66 (1H, t), 7.57-7.63 (2H, m), 7.51 (2H, d), 7.4 6 (2H, d), 6.33 (1H, d), 5.14 (1H, d), 2.62-2.73 (2H, m), 2.51-2.62 (2H, m), 1.13-1.26 (24H, m)

[0225] The first compounds other than Compound B-1 were synthesized with reference to the synthesis method of Compound B-1.

[0226] [Synthesis of Compound R-1] Compound R-1 was synthesized according to the following scheme.

[0227]

[0228] <Synthesis of Compound (R-1-1)> 4H-cyclopenta[2,1-b:3,4-b']dithiophene (11.0 g, 61.7 mmol), methyl p-toluenesulfonate (25.6 g, 148 mmol), potassium iodide (1.02 g, 6.17 mmol), and dimethyl sulfoxide (330 mL) were mixed and stirred at room temperature, and then potassium hydroxide (12.5 g, 222 mmol) was added and stirred at room temperature for 2 hours. The reaction solution was added to water (660 mL) and stirred at room temperature for 1 hour. The precipitate was then collected by filtration and washed with water. The resulting crude product was recrystallized from toluene to obtain compound (R-1-1) (7.65 g, 37.1 mmol).

[0229] <Synthesis of Compound (R-1-2)> Compound (R-1-1) (7.65 g, 35.6 mmol) and DMF (N,N-dimethylformamide, 77 mL) were mixed and stirred at room temperature, and then (chloromethylene)dimethyliminium chloride (5.47 g, 42.7 mmol) was added and stirred at room temperature for 3 hours. After stirring under water cooling, water (230 mL) was added dropwise, and the mixture was stirred at room temperature for 30 minutes. The precipitate was collected by filtration and washed with water to obtain compound (R-1-2) (8.28 g, 99%).

[0230] Synthesis of Compound (R-1-3) Compound (R-1-2) (8.28 g, 35.3 mmol), NBS (6.29 g, 35.3 mmol), and DMF (166 mL) were mixed and stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The precipitate was collected by filtration and washed with water and methanol to obtain (R-1-3) (10.4 g, 94%).

[0231] <Synthesis of Compound (R-1-4)> Compound (R-1-3) (10.4 g, 33.2 mmol), triethyl orthoformate (33.1 mL, 199 mmol), ammonium chloride (1.78 g, 33.2 mmol), and ethanol (208 mL) were mixed and stirred under reflux for 2 hours. The mixture was allowed to cool to room temperature, and triethylamine (6.94 mL, 49.8 mmol) was added to the reaction mixture, followed by stirring at room temperature for 30 minutes. The reaction mixture was diluted with ethyl acetate and hexane, washed with water and saturated brine, and the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting crude product was purified by aminosilica gel chromatography (eluent (volume ratio): hexane / ethyl acetate = 99 / 1) to obtain compound (R-1-3) (12.3 g, 96%).

[0232] <Synthesis of Compound (R-1-5)> Compound (R-1-4) (12.1 g, 31.2 mmol) and THF (241 mL) were mixed and stirred at −78° C., and then a 1.01 M lithium isopropylamide solution in hexane / THF (46.3 mL, 46.7 mmol) was slowly added dropwise thereto, followed by stirring at −78° C. for 1 hour. DMF (6.0 mL, 77.9 mmol) was slowly added dropwise to the reaction solution, and the mixture was heated to 0° C. and stirred for 30 minutes. Saturated saline (120 mL) was slowly added to the reaction solution, followed by stirring at room temperature for 15 minutes. The mixture was extracted with ethyl acetate using a separatory funnel, and the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent (volume ratio): hexane / ethyl acetate / triethylamine=80 / 20 / 2) to obtain compound (R-1-5) (9.35 g, 72%).

[0233] <Synthesis of Compound (R-1-6)> Compound (R-1-5) (4.71 g, 11.3 mmol), ethyl mercaptoacetate (1.86 mL, 17.0 mmol), potassium carbonate (4.70 g, 34.0 mmol), and DMF (113 mL) were mixed and stirred at 50°C for 4 hours. After cooling to room temperature, water (113 mL) was added to the reaction solution, followed by addition of ethyl acetate (56 mL) and hexane (56 mL), and the mixture was stirred at room temperature for 10 minutes. After removing the aqueous layer using a separatory funnel, the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting crude product was recrystallized from dichloromethane and methanol to obtain compound (R-1-6) (4.4 g, 89%).

[0234] <Synthesis of Compound (R-1-7)> Compound (R-1-6) (4.0 g, 9.16 mmol) and THF (40 mL) were mixed and stirred at −10° C., and then a 0.25 M lithium isobutyl-tert-butoxyaluminum hydride solution in hexane / THF (59 mL, 14.7 mmol) was slowly added dropwise, followed by stirring at −10° C. for 1 hour. 1 M hydrochloric acid (40 mL) and 30% hydrochloric acid (10 mL) were slowly added to the reaction solution, and the mixture was warmed to room temperature and stirred for 30 minutes. After removing the aqueous layer using a separatory funnel, the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent (volume ratio): dichloromethane / ethyl acetate = 95 / 5) to obtain compound (R-1-7) (1.50 g, 51%).

[0235] <Synthesis of Compound R-1> Compound (R-1-7) (700 mg, 2.20 mmol), compound (R-1-8) (972 mg, 5.28 mmol), piperidine (43.5 μL, 0.44 mmol), and toluene (35 mL) were mixed and stirred at 100°C for 2 hours. The mixture was allowed to cool to room temperature and concentrated under reduced pressure. The obtained crude product was purified by recrystallization from dichloromethane and methanol. The obtained crude product was then purified by sublimation to obtain compound (1-41) (960 mg, 67%). The obtained compound R-1 was identified by NMR, and the results are as follows: １ H-NMR (CDCl ３, 400MHz); δ = 8.73 (1H, d), 8.72 (1H, d), 8.10 (1H, s), 7.76 (1H, s), 4.02-4.15 (8H, m), 1.67 (6H, s), 1.25-1.36 (12H, m)

[0236] The second compounds other than compound R-1 were synthesized with reference to the synthesis method of compound R-1.

[0237] [Evaluation] The photoelectric conversion element was evaluated for quantum efficiency, response speed, and electric field intensity dependence of quantum efficiency when receiving blue-green light (wavelength 460 nm) or green-red light (wavelength 590 nm) by the following methods.

[0238] [Fabrication of Photoelectric Conversion Element 1] Using the various components shown above, a photoelectric conversion element 1 of the first embodiment, as shown in FIG. 2, was fabricated. Here, the photoelectric conversion element 1 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. The photoelectric conversion film 12 is a mixed layer containing a first compound and a second compound. 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). Next, with the glass substrate at room temperature, a first compound or comparative compound 1 shown in Table 1, a second compound or comparative compound 2 shown in Table 1, and an n-type organic semiconductor (fullerene (C ６０)) and a p-type organic semiconductor (compound (P-1)) were co-deposited by vacuum deposition in a ratio of first compound or comparative compound 1: second compound or comparative compound 2: p-type organic semiconductor: n-type organic semiconductor = 1:1:2:2 (single layer equivalent) to form a photoelectric conversion film 12 (film thickness 320 nm) having a bulk heterostructure. The photoelectric conversion film 12 was a mixed layer containing the first compound and the second compound. At this time, the film formation rate of the photoelectric conversion film 12 was 1.0 Å / sec. Furthermore, compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming an SiO film as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al ２ O ３ The resulting laminate was heated in a glove box at 150° C. for 30 minutes to obtain a photoelectric conversion element 1.

[0239]

[0240] [Dark Current] The dark current of each of the obtained photoelectric conversion elements 1 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.

[0241] [Quantum Efficiency] The quantum efficiency of each photoelectric conversion element 1 was measured when blue-green light or green-red light was received by the following method. ５After applying a voltage to achieve an electric field strength of 1000 V / cm, light was irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency (photoelectric conversion efficiency) at wavelengths of 460 nm and 590 nm, and the quantum efficiency (relative ratio) was calculated according to formula (S1). From the obtained values, the quantum efficiency was evaluated according to the following evaluation criteria. Example 1-1 was used as the reference example. Note that the numerator and denominator of formula (S1) were used to compare photoelectric conversion efficiencies at the same wavelength. For example, the quantum efficiency (relative ratio) at a wavelength of 460 nm in Example 1-2 was calculated by (photoelectric conversion efficiency at a wavelength of 460 nm of the photoelectric conversion element of Example 1-2) / (photoelectric conversion efficiency at a wavelength of 460 nm of the photoelectric conversion element of Example 1-1), and the quantum efficiency (relative ratio) at a wavelength of 590 nm in Example 1-2 was calculated by (photoelectric conversion efficiency at a wavelength of 590 nm of the photoelectric conversion element of Example 1-2) / (photoelectric conversion efficiency at a wavelength of 590 nm of the photoelectric conversion element of Example 1-1). The same applies to formulas (S2) and (S3) below. Formula (S1): Quantum efficiency (relative ratio) = (photoelectric conversion efficiency of each photoelectric conversion element) / (photoelectric conversion efficiency of the photoelectric conversion element of the reference example)

[0242] A: Quantum efficiency (relative ratio) is 0.95 or more. B: Quantum efficiency (relative ratio) is 0.80 or more and less than 0.95. C: Quantum efficiency (relative ratio) is less than 0.80.

[0243] [Response Speed] The response speed of each photoelectric conversion element 1 when receiving blue-green light or green-red light was evaluated by the following method. ５A voltage was applied to the device 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 wavelengths of 460 nm and 590 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity, and the relative response speed was calculated according to formula (S2). From the obtained values, the response speed was evaluated according to the following evaluation criteria. Example 1-1 was used as the reference example. Note that the numerator and denominator of formula (S2) were used to compare the rise times at the same wavelength. It is preferable that the response speed be rated B or higher. Formula (S2): Relative response speed = (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element of the reference example)

[0244] A: Relative response speed is less than 1.1 B: Relative response speed is 1.1 or more and less than 1.5 C: Relative response speed is 1.5 or more

[0245] [Dependence of Quantum Efficiency on Electric Field Intensity] The dependence of quantum efficiency on electric field intensity when blue-green light or green-red light was received was evaluated for each photoelectric conversion element 1 by the following method. In the evaluation of [Quantum Efficiency], the voltage applied to each photoelectric conversion element 1 was 5.0×10 ４ The same procedure was followed except that the pressure was changed to 5.0 × 10 ４ The photoelectric conversion efficiency at 1000 V / cm was measured. The electric field strength dependency of quantum efficiency was calculated according to formula (S3), and the electric field strength dependency of quantum efficiency was evaluated according to the following evaluation criteria. In formula (S3), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. The numerator and denominator of formula (S3) were used to compare photoelectric conversion efficiencies at the same wavelength. For example, the electric field strength dependency of quantum efficiency at a wavelength of 460 nm in Example 1-1 was calculated as follows (when the electric field strength of the photoelectric conversion element of Example 1-1 was 5.0 × 10 ４ Quantum efficiency at a wavelength of 460 nm when the photoelectric conversion element is 1.0 V / cm) / (electric field strength of the photoelectric conversion element of Example 1-1 2.0 × 10 ５The quantum efficiency is calculated using the following formula (S3): electric field strength dependence of quantum efficiency = (applied voltage of each photoelectric conversion element 5.0 × 10) ４ V / cm) / (applied voltage of each photoelectric conversion element 2.0×10 ５ Photoelectric conversion efficiency in V / cm

[0246] A: The electric field strength dependency of quantum efficiency is 0.90 or more. B: The electric field strength dependency of quantum efficiency is 0.85 or more and less than 0.90. C: The electric field strength dependency of quantum efficiency is less than 0.85.

[0247] [result]

[0248] The evaluation results are shown in Table 1 below. In the table, the "Formula" column of the "First Compound" column lists the formula number to which the first compound corresponds. For example, in the case of a compound represented by formula (4), "(4)" is listed; in the case of a compound represented by formula (1) but not a compound represented by formula (4), "(1)" is listed; in the case of a compound represented by formula (5), "(5)" is listed; and in the case of a compound represented by formula (2) but not a compound represented by formula (5), "(2)" is listed. In the table, in the "n=1" column, if the second compound is a compound where n=1, "A" is listed; otherwise, "B" is listed. In the table, in the "k=1,2" column, if the second compound is a compound where k=1 or 2, "A" is listed; otherwise, "B" is listed. In the table, in the "A=(A-1)" column, if the second compound is A, ３１ and A ３２ is a compound of the group represented by formula (A-1), it is designated as "A", and in other cases it is designated as "B".

[0249]

[0250] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention has a small dependence of quantum efficiency on electric field strength when receiving blue-green light, and a small dependence of quantum efficiency on electric field strength when receiving green-red light.

[0251] A comparison of Examples 1-1 to 1-13 confirmed that when the first compound is a compound represented by formula (4) or a compound represented by formula (5), the response speed is superior and the dependence of the quantum efficiency on the electric field strength is smaller. A comparison of Examples 1-3 and 1-5 with other Examples confirmed that when the substituent of the aryl group is an alkyl group having two or more carbon atoms, the quantum efficiency when blue-green light is received is superior. A comparison of Examples 1-17 and 1-16 confirmed that when X Ｉ is an oxygen atom, a sulfur atom, or -CR Ａ４ ２ -, it was confirmed that the quantum efficiency when green and red light was received was better. From a comparison between Examples 1-19 to 1-22 and Examples 1-14 to 1-18, it was confirmed that when n = 1 in formula (3), the quantum efficiency when green and red light was received was better and the dependence of the quantum efficiency on the electric field strength was smaller. From a comparison between Examples 1-23 to 1-24 and Examples 1-19 to 1-22, it was confirmed that when k = 1 or 2 in formula (3), the response speed was better. From a comparison between Example 1-14 and Examples 1-23 to 1-24, it was confirmed that when A １ and A ２ is a group represented by formula (A-1), it has been confirmed that the quantum efficiency when receiving green and red light is superior.

[0252] [Fabrication of Photoelectric Conversion Element 2] A photoelectric conversion element 2 of the second embodiment shown in FIG. 2 was fabricated using the various components shown in Table 1 above. Here, the photoelectric conversion element 2 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. The photoelectric conversion film 12 is a laminated film in which, from the electron blocking film 16A side, a first film containing a first compound and a second film containing a second compound are laminated. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and further a film of compound (EB-1) was formed on the lower electrode 11 by vacuum heating evaporation to form an electron blocking film 16A (thickness: 30 nm). Next, with the glass substrate at room temperature, a mixture of the first compound or comparative compound 1 shown in Table 1 and an n-type organic semiconductor (fullerene (C６０ )) and a p-type organic semiconductor (compound (P-1)) were co-deposited by vacuum deposition in a ratio of first compound or comparative compound 1:p-type organic semiconductor:n-type organic semiconductor = 1:1:1 (single layer equivalent) to form a first film (thickness 160 nm) having a bulk heterostructure. Furthermore, on the formed first film, a second compound or comparative compound 2 shown in Table 1 and an n-type organic semiconductor (fullerene (C ６０ )) and a p-type organic semiconductor (compound (P-1)) were co-deposited by vacuum deposition in a ratio of second compound or comparative compound 2:p-type organic semiconductor:n-type organic semiconductor = 1:1:1 (single layer equivalent) to form a second film (thickness 160 nm) having a bulk heterostructure. This resulted in a photoelectric conversion film 12 (thickness 320 nm) having a stacked structure of a first film (thickness 160 nm) containing the first compound and a second film (thickness 160 nm) containing the second compound. The deposition rate of the first film and the second film was 1.0 Å / sec. Compound (EB-2) was further deposited on the photoelectric conversion film 12 to form a hole-blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole-blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming an SiO film 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 2.

[0253] Each of the obtained photoelectric conversion elements 2 was evaluated in the same manner as for the photoelectric conversion element 1, and the results showed the same tendency as those shown in Table 1.

[0254] 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 first compound represented by formula (1) or formula (2) and a second compound represented by formula (3). In formula (1), R １１ and R １２ R each independently represents a hydrogen atom or a substituent. ａ１１ and R ａ１２ each independently represents an optionally substituted aryl group, —C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ), or a heteroaryl group which may have a substituent. Ｌ１１ ~R Ｌ１３ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, provided that R Ｌ１１ ~R Ｌ１３ At least two of R represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Ｌ１１ ~R Ｌ１３ The alkyl group which may have a substituent, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent, which are represented by the following formula (1), may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. １１ represents an aromatic ring which may have a substituent. ２１ and R ２２ R each independently represents a hydrogen atom or a substituent. ２３ and R ２４ R each independently represents a substituent. ２３ and R ２４ may be bonded to each other to form a ring which may have a substituent. ａ２ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ２１ represents an aromatic ring which may have a substituent. ２１ represents a monocyclic ring having 5 or more ring atoms which may have a substituent. ２１ and Z ２２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｙ１ , or =CR Ｙ２ R Ｙ３ Represents R Ｙ１ represents a hydrogen atom or a substituent. Ｙ２ and R Ｙ３ each independently represents a cyano group, —COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ Represents R Ｙ４ ~R Ｙ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. ３１ represents a group represented by formula (D-1) to formula (D-3), where n D ３１ At least one of the groups represented by formula (D-1) is a group represented by formula (D-1). n represents an integer of 1 to 3. When n is 2 or 3, a plurality of D ３１ may be the same or different. ３１ and A ３２ each independently represents a group represented by formula (A-1) or formula (A-2). In formula (D-1), k represents an integer of 0 to 4. W １ａ and W ２ａ are each independently -Z ａ =Z ａ -C(*)=Z ａ - or -Z ａ = C(*)-X ａ - represents Y １ａ and Y ２ａ is one of the following combinations 1 to 4. Combination 1: Y １ａ and Y ２ａ are each independently -Z ａ = Combination 2: Y １ａ and Y ２ａ One of them is -Z ａ =Z ａ - and the other represents a single bond. １ａ and Y ２ａ One of them is -X ａ - and the other represents a single bond. １ａ and Y ２ａ One of the two is -C(T １ａ ) (T ２ａ )-Y ａ -, or -C(=X ｂ )-Y ａ - and the other represents a single bond. ａ are each independently -CR Ａ = or represents a nitrogen atom. Ａ represents a hydrogen atom or a substituent. ａ represents an oxygen atom, a sulfur atom, a selenium atom, -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ )-. Ａ１ ~R Ａ５ R each independently represents a hydrogen atom or a substituent. Ａ２ Comrade, R Ａ３ Comrade, R Ａ４ Peers and R Ａ５ and may be bonded to each other to form a ring which may have a substituent. １ａ and T ２ａ each independently represents a hydrogen atom or a substituent. ａ represents an oxygen atom, a sulfur atom, or —NR Ａ１ - represents X ｂ represents an oxygen atom or a sulfur atom. １ａ ~Z ６ａ Two of them represent -C(*)=, and four of them are each independently -CR Ａ In formula (D-3), Z represents a nitrogen atom. １１ａ ~Z １５ａ Two of them represent -C(*)=, and two of them are independently -CR Ａ = or a nitrogen atom, and one represents an oxygen atom, a sulfur atom, a selenium atom, or -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ In formula (A-1), C １ represents a ring containing two or more carbon atoms and which may have a substituent. １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ１ , or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ represents a hydrogen atom or a substituent. Ｗ２ and R Ｗ３ each independently represents a cyano group, —COOR Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ Represents R Ｗ４ ~R Ｗ６ 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. Ａ１ and R ａ２ each independently represents a cyano group, —COOR ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents R ｂ１ ~R ｂ４ 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. * represents a bonding position.

2. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion film has a mixed layer formed in a state where the first compound and the second compound are mixed.

3. The photoelectric conversion element according to claim 2, wherein the mixed layer further contains an n-type organic semiconductor, and the mixed layer has a bulk heterostructure formed by mixing the first compound, the second compound, and the n-type organic semiconductor.

4. The photoelectric conversion element according to claim 3, wherein the mixed layer further contains a p-type organic semiconductor, and the mixed layer has a bulk heterostructure formed by mixing the first compound, the second compound, the n-type organic semiconductor, and the p-type organic semiconductor.

5. The photoelectric conversion element according to claim 3, wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof.

6. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion film has a first layer containing the first compound and a second layer containing the second compound.

7. The photoelectric conversion element according to claim 6, wherein the first layer and the second layer further contain an n-type organic semiconductor, the first layer has a bulk heterostructure formed by mixing the first compound with the n-type organic semiconductor, and the second layer has a bulk heterostructure formed by mixing the second compound with the n-type organic semiconductor.

8. The photoelectric conversion element according to claim 7, wherein the first layer and the second layer further contain a p-type organic semiconductor, the first layer has a bulk heterostructure formed by a mixture of the first compound, the n-type organic semiconductor, and the p-type organic semiconductor, and the second layer has a bulk heterostructure formed by a mixture of the second compound, the n-type organic semiconductor, and the p-type organic semiconductor.

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

10. The photoelectric conversion element according to claim 1, wherein the content of said first compound relative to the content of said second compound in said photoelectric conversion film is 40 to 240% by volume.

11. The photoelectric conversion element according to claim 1, wherein the first compound has a maximum absorption wavelength in the range of 400 to 500 nm, and the second compound has a maximum absorption wavelength in the range of 500 to 650 nm.

12. The photoelectric conversion element according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (4), and the compound represented by formula (2) is a compound represented by formula (5). In formula (4), R ４１ and R ４２ R each independently represents a hydrogen atom or a substituent. ４３ ~R ４６ R each independently represents a hydrogen atom or a substituent. ａ４１ and R ａ４２ each independently represents an optionally substituted aryl group, —C(R Ｌ４１ ) (R Ｌ４２ ) (R Ｌ４３ ), or a heteroaryl group which may have a substituent. Ｌ４１ ~R Ｌ４３ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, provided that R Ｌ４１ ~R Ｌ４３ At least two of R represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Ｌ４１ ~R Ｌ４３ The alkyl group which may have a substituent, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent, which are represented by the formula (5), may be bonded to each other via a single bond or a divalent linking group to form a ring which may have a substituent. ５１ and R ５２ R each independently represents a hydrogen atom or a substituent. ５３ and R ５４ R each independently represents a substituent. ５３ and R ５４ may be bonded to each other to form a ring which may have a substituent. ａ５ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, provided that R ａ５ represents an alkyl group which may have a substituent, R ５３ and R ５４ each independently represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, or R ５３ and R ５４ are bonded to each other to form a ring which may have a substituent. ５５ ~R ５８ each independently represents a hydrogen atom or a substituent. ５１ represents a monocyclic ring having 5 or more ring atoms which may have a substituent. ５１ and Z ５２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｙ１ , or =C(R Ｙ２ ) (R Ｙ３ ) represents. Ｙ１ represents a hydrogen atom or a substituent. Ｙ２ and R Ｙ３ each independently represents a cyano group, —COOR Ｙ４ , -COR Ｙ５ , or -SO ２ R Ｙ６ Represents R Ｙ４ ~R Ｙ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

13. The photoelectric conversion element according to claim 1, wherein n is 1 in the formula (3).

14. The photoelectric conversion element according to claim 1, wherein in formula (D-1), k is 1 or 2.

15. In the formula (3), A ３１ and A ３２ each independently represents a group represented by formula (A-1), 16. The photoelectric conversion element according to any one of claims 1 to 15, further comprising one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

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

18. An optical sensor comprising the photoelectric conversion element according to any one of claims 1 to 15.

19. A method for manufacturing an imaging element, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 15.

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