Photoelectric conversion elements, imaging elements, optical sensors, compounds

Abstract

To provide a photoelectric conversion element that has high photoelectric conversion efficiency in a visible light region (particularly in a wavelength region of 450 to 650 nm) even after being subjected to heat treatment (annealing).SOLUTION: A photoelectric conversion element 10a includes a conductive film 11, an electron blocking film 16A, a photoelectric conversion film 12, and a transparent conductive film 15 in this order, and the photoelectric conversion film 12 contains at least a compound represented by a following formula (1).SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] In recent years, development of elements (for example, imaging elements) having photoelectric conversion films has progressed. For example, Patent Document 1 discloses the following compound as a material to be applied to a photoelectric conversion element.

[0003] [ka] [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 013246 Summary of the Invention [Problem to be solved by the invention]

[0005] 2. Description of the Related Art In recent years, with the demand for improved performance of image pickup devices, optical sensors, and the like, further improvements in the properties required of the photoelectric conversion elements used therein have been demanded. The present inventors fabricated and examined a photoelectric conversion element using the compound disclosed in Patent Document 1, and found that the photoelectric conversion efficiency in the visible light region (particularly, the wavelength region of 450 to 650 nm) of the photoelectric conversion element that had been subjected to heat treatment (annealing) did not meet the desired required level, and further improvement was necessary. In other words, it became clear that there is room for development of a photoelectric conversion element that has high photoelectric conversion efficiency in the visible light region (particularly, the wavelength region of 450 to 650 nm) even after being subjected to heat treatment (annealing).

[0006] Therefore, an object of the present invention is to provide a photoelectric conversion element that has high photoelectric conversion efficiency in the visible light region (particularly, the wavelength region of 450 to 650 nm) even after heat treatment (annealing). Another object of the present invention is to provide an imaging element, an optical sensor, and a compound. [Means for solving the problem]

[0007] As a result of extensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a compound having a specific structure in a photoelectric conversion film, and have thus completed the present invention.

[0008] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, The photoelectric conversion element, wherein the photoelectric conversion film contains at least a compound represented by formula (1) described below. [2] The above Y 11 and the above Y 12 represents an oxygen atom or a sulfur atom, Above Y 21 and the above Y 22

[0023] The photoelectric conversion element according to [1], wherein one of the groups represents an oxygen atom or a sulfur atom. [3] The above Y 11 and the above Y 12 one of the groups represents =C(CN)2, Above Y 21 and the above Y 22 The photoelectric conversion element according to [1], wherein one of the groups represents =C(CN)2. [4] A above 1 represents a group represented by formula (1Aa-1) described below. The photoelectric conversion element according to any one of [1] to [3]. [5] D above 1 represents a group represented by either formula (1D) or formula (2D) described later. [6] D above 1 represents a group represented by the above formula (1D). [7] The photoelectric conversion element according to [6], wherein the group represented by the formula (1D) above is a group represented by the formula (3D) described below. [8] The photoelectric conversion element according to [6], wherein the group represented by the formula (1D) above is a group represented by the formula (4D) described below. [9] The photoelectric conversion element according to [6], wherein the group represented by the formula (1D) is a group represented by the formula (5D) described below.

[10] R above d11 and the above R d12 The photoelectric conversion element according to any one of [1] to [9], wherein the and have different structures.

[11] R above d11 and the above R d12 The photoelectric conversion element according to any one of [1] to

[10] , wherein one of the groups represents an alkyl group which may have a substituent, and the other represents a group represented by formula (X) described below.

[12] The photoelectric conversion element according to

[11] , wherein the group represented by the formula (X) represents a group represented by the formula (ZB) described below.

[13] D above 1 represents a group represented by the above formula (2D), The photoelectric conversion element according to [5], wherein the group represented by the formula (2D) above is a group represented by the formula (6D) described below.

[14] The photoelectric conversion element according to

[13] , wherein the formula (6D) satisfies at least one of the following requirements: Requirement X1: Above R d22 represents an aromatic ring group which may have a substituent. Requirement X2: Above X d21 -C(R L24 )(R L25 )- and R L24 and R L25 and are bonded to each other to form a ring. Requirement X3: Above R d61 and the above R d62 , the above R d62 and the above R d63 , and the above R d63 and the above R d64 Any one or more of the following may be bonded to each other to form a ring.

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

[14] , wherein the photoelectric conversion film further contains an n-type semiconductor.

[16] The photoelectric conversion element according to

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

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

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

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

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

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

[18] .

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

[19] .

[21] A compound represented by the formula (1) described below. 〔twenty two〕 Above Y 11 and the above Y 12 represents an oxygen atom or a sulfur atom, Above Y 21 and the above Y 22

[21] The compound according to

[21] , wherein one of represents an oxygen atom or a sulfur atom.

[23] Y above 11 and the above Y 12 one of the groups represents =C(CN)2, Above Y 21 and the above Y 22 The compound according to

[21] , wherein one of the following represents =C(CN)2.

[24] Above A 1 represents a group represented by formula (1Aa-1) described below.

[25] D above 1 represents a group represented by either formula (1D) or formula (2D) described later.

[26] D above 1 represents a group represented by the above formula (1D).

[27] The compound according to

[26] , wherein the group represented by the formula (1D) above is a group represented by the formula (3D) described below.

[28] The compound according to

[26] , wherein the group represented by the formula (1D) above is a group represented by the formula (4D) described below.

[29] The compound according to

[26] , wherein the group represented by the formula (1D) is a group represented by the formula (5D) described below.

[30] R above d11 and the above R d12 and have different structures.

[31] R above d11 and the above R d12 The compound according to any one of

[21] to

[30] , wherein one of the groups represents an alkyl group which may have a substituent, and the other represents a group represented by formula (X) described below.

[32] The compound according to

[31] , wherein the group represented by the formula (X) above is a group represented by the formula (ZB) described below.

[33] D above 1 represents a group represented by the above formula (2D), The compound according to

[25] , wherein the group represented by the formula (2D) above is a group represented by the formula (6D) described below.

[34] The compound according to

[33] , wherein the formula (6D) satisfies at least one of the following requirements: Requirement X1: Above R d22 represents an aromatic ring group which may have a substituent. Requirement X2: Above X d21 -C(R L24 )(R L25 )- and R L24 and R L25 and are bonded to each other to form a ring. Requirement X3: Above R d61 and the above R d62 , the above R d62 and the above R d63 , and the above R d63 and the above R d64 Any one or more of the following may be bonded to each other to form a ring. [Effects of the Invention]

[0009] According to the present invention, a photoelectric conversion element having high photoelectric conversion efficiency in the visible light region (particularly, a wavelength region of 450 to 650 nm) even after heat treatment (annealing) can be provided. Furthermore, according to the present invention, an imaging element, an optical sensor, and a compound can also be provided. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a cross-sectional view showing a configuration example of a photoelectric conversion element. [Figure 2] FIG. 2 is a cross-sectional view showing a configuration example of a photoelectric conversion element. DETAILED DESCRIPTION OF THE INVENTION

[0011] Preferred embodiments of the photoelectric conversion element of the present invention will be described below. 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. In this specification, when there are a plurality of substituents, linking groups, etc. (hereinafter also referred to as "substituents, etc.") represented by a specific symbol, or when a plurality of substituents, etc. are simultaneously specified, it means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc. In this specification, the hydrogen atom may be a protium atom (normal hydrogen atom) or a deuterium atom (for example, a deuterium atom, etc.). In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. In this specification, unless otherwise specified, examples of the "substituent" include the groups exemplified as the substituent W described below.

[0012] (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 heteroaryl group (which may also be called a heterocyclic group), a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, Examples of the W substituent include secondary or tertiary amino groups (including anilino groups), alkylthio groups, arylthio groups, heterocyclic thio groups, alkyl or arylsulfinyl groups, alkyl or arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, aryl or heterocyclic azo groups, imido groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, silyl groups, carboxy groups, phosphate groups, sulfonic acid groups, hydroxy groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, boronic acid groups, and primary amino 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 that may have a substituent is also included as one form of the substituent W. When the substituent W has a carbon atom, the number of carbon atoms contained in the substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30. It is also preferable that the specific compound does not have a carboxy group, a salt of a carboxy group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH)2), and / or a primary amino group as a substituent.

[0013] In this specification, unless otherwise specified, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. 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 i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and a cyclopentyl group. The alkyl group may be, for example, a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have these cyclic structures as partial structures. In the alkyl group which may have a substituent, the substituent which the alkyl group may have is not particularly limited, and examples thereof include the substituent W, and 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.

[0014] In this specification, unless otherwise specified, the alkyl group moiety in an alkoxy group is preferably the above-mentioned alkyl group, and the alkyl group moiety in an 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 substituents 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 substituents in the alkyl group which may have a substituent.

[0015] 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, more preferably 2 to 12, still more preferably 2 to 6, and particularly preferably 2 to 3. In the alkenyl group which may have a substituent, examples of the substituent which the alkenyl group may have include the same as the substituent 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, more preferably 2 to 12, still more preferably 2 to 6, and particularly preferably 2 to 3. In the alkynyl group which may have a substituent, examples of the substituent which the alkynyl group may have include the same as the substituent in the alkyl group which may have a substituent.

[0016] In this specification, unless otherwise specified, examples of the silyl group which may have a substituent include, for example, —Si(R S1 )(R S2 )(R S3 ) is an example of a group represented by R S1 , R S2 and R S3 each independently represents a hydrogen atom or a substituent, and preferably represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

[0017] In this specification, unless otherwise specified, the aromatic ring 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 aromatic ring (e.g., 2 to 6 rings) is an aromatic ring having a plurality of (e.g., 2 to 6) condensed aromatic ring structures as a ring structure. The aromatic ring preferably has 5 to 15 ring atoms. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. When the aromatic ring is an aromatic heterocycle, 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, and a phenanthrene ring. Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (such as a 1,2,3-triazine ring, a 1,2,4-triazine ring, or a 1,3,5-triazine ring), a tetrazine ring (such as 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 3H-pyrrolidine ring, a pyrroloimidazole ring (such as a 5H-pyrrolo[1,2-a]imidazole ring), an imidazooxazole ring (such as an imidazo[2,1-b]oxazole ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring (such as a 5H-pyrrolo[1,2-a]imidazole ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene 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 3H-pyrrolidine ring, a pyrroloimidazole ring (such as a 5H-pyrrolo[1,2-a]imidazole ring), a quinoxaline ring, a pyrrole ring, a pyrimidine thiazolo ring, etc.), thienothiazole ring (thieno[2,3-d]thiazole ring, etc.), benzothiadiazole ring, benzodithiophene ring (benzo[1,2-b:4,5-b']dithiophene ring, etc.), thienothiophene ring (thieno[3,2-b]thiophene ring, etc.), thiazolothiazole ring (thiazolo[5,4-d]thiazole ring, etc.), naphthodithiophene ring (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, 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. In the aromatic ring which may have a substituent, the type of the substituent which the aromatic ring may have is not particularly limited, and examples thereof include a substituent W. When the aromatic ring has a substituent, the number of the substituents may be 1 or more (e.g., 1 to 4). In this specification, the term "aromatic ring group" includes, for example, a group obtained by removing one or more (for example, 1 to 5) hydrogen atoms from the above-mentioned aromatic ring. In this specification, the term "aryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring that corresponds to an aromatic hydrocarbon ring among the above aromatic rings. In this specification, the term "heteroaryl group" refers to, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic heterocycle among the above aromatic rings. In this specification, the term "arylene group" refers to, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above aromatic rings. As used herein, the term "heteroarylene group" refers to, for example, a group formed by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above aromatic rings. In the aromatic ring group which may have a substituent, the aryl group which may have a substituent, the heteroaryl group which may have a substituent, the arylene group which may have a substituent, and the heteroarylene group which may have a substituent, the type of substituent that these groups may have is not particularly limited, and examples thereof include the substituent W. When these groups which may have a substituent have a substituent, the number of the substituent may be 1 or more (e.g., 1 to 4).

[0018] In this specification, when a formula (general 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 same symbols may be the same or different, unless otherwise specified. In this specification, when a formula (general formula) showing a chemical structure contains a plurality of groups of the same type (such as alkyl groups), the specific details of the plurality of groups of the same type are independent of each other, and the specific details of the groups of the same type may be the same or different.

[0019] The bonding direction of a divalent group (e.g., -CO-O-) represented in this specification is not limited unless otherwise specified. For example, when Y in a compound represented by the general formula "XYZ" is -CO-O-, the compound may be "XO-CO-Z" or "X-CO-OZ."

[0020] In this specification, with respect to a compound 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.

[0021] [Photoelectric conversion element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) described below (hereinafter also referred to as a "specific compound"). The mechanism by which the photoelectric conversion element of the present invention having such a configuration can solve the above problems is not entirely clear, but the present inventors speculate as follows. The main feature of the specific compound is that it has a DA (donor-acceptor) structure and 1 (acceptor moiety) is a group represented by formula (1A) or formula (2A) described later. More specifically, the specific compound is 11 and Y 12 and Y in formula (2A). 21 and Y 22 The structures of A and B are different from each other (asymmetric structures), and 1 (acceptor moiety) is a five-membered aromatic ring structure (X in formula (1A) 11 ~X 13 and X 11 and X 13 a five-membered aromatic ring structure in which each carbon atom adjacent to 21 ~X 23 and X 21 and X 23The specific compound has an absorption band over a wide wavelength range in the visible light region (particularly, a wavelength range of 450 to 650 nm) due to the above structure. Furthermore, it is believed that the specific compound is less likely to aggregate even when subjected to heat treatment (annealing treatment), resulting in excellent uniformity within the film. As a result, it is presumed that the photoelectric conversion element of the present invention has small wavelength dependency of photoelectric conversion efficiency and also exhibits high photoelectric conversion efficiency even after heat treatment (annealing treatment).

[0022] Hereinafter, the term "better effects of the present invention" refers to a photoelectric conversion element having better photoelectric conversion efficiency after heat treatment (annealing treatment), a photoelectric conversion element having better fluctuations in photoelectric conversion efficiency due to heat treatment (annealing treatment), a photoelectric conversion element having better response speed, and / or a photoelectric conversion element having better suppression of the electric field strength dependency of the response speed.

[0023] FIG. 1 shows a cross-sectional view of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 functioning as an upper electrode are stacked in this order. Fig. 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in Fig. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figs. 1 and 2 may be changed as appropriate depending on the application and characteristics.

[0024] In the photoelectric conversion element 10a (or 10b), it is preferable that light be incident on the photoelectric conversion film 12 through the upper electrode 15. Furthermore, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage is applied between this pair of electrodes. The voltage is 1.0 x 10 -5 ~1.0×10 7 V / cm is preferred, and from the viewpoint of performance and power consumption, 1.0×10 -4 ~1.0×10 7 V / cm is more preferable, and 1.0×10 -3 ~5.0×10 6 V / cm is more preferred. 1 and 2, the voltage is preferably applied so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode. When the photoelectric conversion element 10a (or 10b) is used as an optical sensor 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.

[0025] The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0026] [Photoelectric conversion film] The photoelectric conversion film is a film containing a specific compound. The specific compounds are described in detail below.

[0027] <Compound represented by formula (1) (specific compound)> The specific compound is a compound represented by formula (1).

[0028] [ka]

[0029] In formula (1), A 1 represents a group represented by either formula (1A) or formula (2A). The group represented by formula (1A) and the group represented by formula (2A) will be described below.

[0030] In formula (1A), Y 11 and Y 12 are each independently an oxygen atom, a sulfur atom, ═C(CN)2, ═C(COR 11 )2, =C(SO2R 11 )2, =C(SOR 11 )2, =C(CN)(COR 11 ), =C(CN)(SO2R 11 ), =C(CN)(SOR 11 ), =C(COR 11 )(SO2R 11 ), =C(COR 11 )(SOR 11 ), or =C(SO2R 11 )(SOR 11 ) where Y 11 and Y 12 are not identical to each other.

[0031] R 11 each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heteroaryl group. R 11 Examples of the hydrocarbon group represented by the formula include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0032] Y 11 and Y 12 As a preferred embodiment of the present invention, Y 11 and Y 12 represents an oxygen atom or a sulfur atom. Y 11 and Y 12 In another preferred embodiment, Y 11 and Y 12 In one embodiment, one of the groups represents =C(CN)2. Among them, Y is the most effective in the present invention. 11 and Y 12 Among these, it is preferred that one represents an oxygen atom or a sulfur atom and the other represents =C(CN)2, and it is more preferred that one represents an oxygen atom and the other represents =C(CN)2.

[0033] X 11 and X 12 one of which is a sulfur atom, an oxygen atom, a selenium atom, or NR 12 and the other represents a nitrogen atom or -CR x = represents. The effects of the present invention are more excellent, especially in X 11 and X 12 One of them represents a sulfur atom, and the other represents a nitrogen atom or -CR x = is preferred, and X 11 and X 12 One represents a sulfur atom and the other represents -CR x It is more preferable to represent =. X 13 -CR x = or represents a nitrogen atom. X 13 As for the effect of the present invention, -CR is more excellent. x It is preferable to represent =.

[0034] R 12 represents a hydrogen atom or a substituent. 12 is preferably a hydrogen atom. R x represents a hydrogen atom or a substituent. x Among these, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom, or a cyano group is preferable, a hydrogen atom, a halogen atom, or a cyano group is more preferable, a hydrogen atom or a halogen atom is still more preferable, and a hydrogen atom or a chlorine atom is particularly preferable. x If there is R x They may be the same or different from each other.

[0035] X 11 and X 13 Ga-CR x =, R x may be linked to each other to form a ring. 12 and X 13 Ga-CR x =, R xThey may be linked to each other to form a ring. The ring may be an aromatic ring or an alicyclic ring, but is preferably an aromatic ring, and more preferably an aromatic hydrocarbon ring. The ring preferably has six members. The ring atoms may contain heteroatoms. 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. Of these, the ring is preferably a benzene ring which may have a substituent. The ring may further have a substituent, and among these, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), or a cyano group is preferable as the substituent.

[0036] In formula (1A), * represents a bonding position.

[0037] The dotted line in formula (1A) indicates X in formula (1A). 11 ~X 13 and X 11 and X 13 represents that the ring structure having each carbon atom adjacent to the ring as a member atom forms a resonance structure (in other words, the ring structure is an aromatic ring). For example, X 11 is a nitrogen atom or -CR x = represents X 12 is a sulfur atom, an oxygen atom, a selenium atom, or NR 12 In the case where * and Y in formula (1Aa) are each independently a substituted or unsubstituted alkyl group, an example of the group represented by formula (1A) is a group represented by formula (1Aa) below. 11 , Y 12 , R x , X 11 , and X 12 is as described above.

[0038] [ka]

[0039] In the formula (1A), as described above, the effect of the present invention is more excellent, and therefore, Y 11 and Y 12 Preferably, one of these groups represents an oxygen atom or a sulfur atom, and the other represents =C(CN)2. In addition, in the formula (1A), for example, Y 11 is an oxygen atom or a sulfur atom, Y 12 If =C(CN)2, then X 11 is a nitrogen atom or -CR x = represents X 12 is a sulfur atom, an oxygen atom, a selenium atom, or NR 12 It is preferable to represent X 11 is a nitrogen atom or -CR x = represents X 12 more preferably represents a sulfur atom, and X 11 -CR x = represents X 12 More preferably, X represents a sulfur atom. 13 As for -CR x It is preferable to represent =.

[0040] In addition, as the group represented by formula (1A), in terms of the effects of the present invention being more excellent, the group represented by the above formula (1Aa), 11 represents an oxygen atom, and Y 12 represents =C(CN)2, and X 11 Ga-CR x = represents X 12 represents a sulfur atom (provided that R x are preferably bonded to each other to form a ring. Specifically, the group represented by formula (1A) is preferably a group represented by the following formula (1Aa-1).

[0041] [ka] (1Aa-1) Medium, R x represents a hydrogen atom or a substituent.

[0042] In formula (2A), Y21 and Y 22 are each independently an oxygen atom, a sulfur atom, ═C(CN)2, ═C(COR 21 )2, =C(SO2R 21 )2, =C(SOR 21 )2, =C(CN)(COR 21 ), =C(CN)(SO2R 21 ), =C(CN)(SOR 21 ), =C(COR 21 )(SO2R 21 ), =C(COR 21 )(SOR 21 ), or =C(SO2R 21 )(SOR 21 ) where Y 21 and Y 22 are not identical to each other.

[0043] R 21 each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heteroaryl group. R 21 Examples of the hydrocarbon group represented by the formula include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0044] Y 21 and Y 22 As a preferred embodiment of the present invention, Y 21 and Y 22 represents an oxygen atom or a sulfur atom. Y 21 and Y 22 In another preferred embodiment, Y 21 and Y 22 In one embodiment, one of the groups represents =C(CN)2. Among them, Y is the most effective in the present invention. 21 and Y 22 Among these, it is preferred that one represents an oxygen atom or a sulfur atom and the other represents =C(CN)2, and it is more preferred that one represents an oxygen atom and the other represents =C(CN)2.

[0045] B represents an optionally substituted 5- or 6-membered monocyclic aromatic ring. Specific examples of the 5- or 6-membered monocyclic aromatic ring represented by B include groups represented by the following formulae (1B) to (3B).

[0046] [ka]

[0047] In formula (1B), X b1 and X b2 are each independently -CR z1 = or represents a nitrogen atom. R z1 represents a hydrogen atom or a substituent. X b1 and X b2 As for the effects of the present invention, both are -CR z1 It is preferable that the two R z1 If there are two R z1 may be the same or different. * indicates the bond position.

[0048] In formula (2B), X b3 is a sulfur atom, an oxygen atom, a selenium atom, -CR z2 R z3 -, -SiR z4 R z5 - or -GeR z6 R z7 - represents. X b3 Among these, a sulfur atom is preferable as the . R z2 ~R z7 each independently represents a hydrogen atom or a substituent. * indicates the bond position.

[0049] In formula (3B), X b4 and X b5 are each independently -CR z8 = or represents a nitrogen atom. R z8represents a hydrogen atom or a substituent. X b4 and X b5 As for the effects of the present invention, both are -CR z8 In addition, it is preferable that two R z8 If there are two R z8 may be the same or different. * indicates the bond position.

[0050] As described above, * in the groups represented by formulae (1B) to (3B) represents a bonding position, and at this bonding position, B is bonded to two 5-membered rings adjacent to B to form a polycyclic structure. Examples of this polycyclic structure include structures represented by formulae (2Aa) to (2Ae) shown in the latter part.

[0051] X 21 and X 22 one of which is a sulfur atom, an oxygen atom, a selenium atom, or NR 22 and the other represents a nitrogen atom or -CR y = represents. The effects of the present invention are more excellent, especially in X 21 and X 22 One of them represents a sulfur atom, and the other represents a nitrogen atom or -CR y = is preferred, and X 21 and X 22 One represents a sulfur atom and the other represents -CR y It is more preferable to represent =. X 23 -CR y = or represents a nitrogen atom. X 23 As for the effect of the present invention, -CR is more excellent. y It is preferable to represent =.

[0052] R 22 represents a hydrogen atom or a substituent. 22 is preferably a hydrogen atom. R y represents a hydrogen atom or a substituent. yAmong these, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom, or a cyano group is preferable, a hydrogen atom, a halogen atom, or a cyano group is more preferable, a hydrogen atom or a halogen atom is still more preferable, and a hydrogen atom or a chlorine atom is particularly preferable. y If there is R y They may be the same or different from each other.

[0053] X 21 and X 23 Ga-CR y =, R y may be linked to each other to form a ring. 22 and X 23 Ga-CR y =, R y They may be linked to each other to form a ring. The ring may be an aromatic ring or an alicyclic ring, but is preferably an aromatic ring, and more preferably an aromatic hydrocarbon ring. The ring preferably has six members. The ring atoms may contain heteroatoms. 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. Of these, the ring is preferably a benzene ring which may have a substituent. The ring may further have a substituent, and among these, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), or a cyano group is preferable as the substituent.

[0054] The dotted line in formula (2A) indicates X in formula (2A). 21 ~X 23 and X 21 and X 23 represents that the ring structure having each carbon atom adjacent to the ring as a member atom forms a resonance structure (in other words, the ring structure is an aromatic ring). For example, X 21 is a nitrogen atom or -CRy = represents X 22 is a sulfur atom, an oxygen atom, a selenium atom, or NR 22 In the case where * and Y in the formula (2Aa) to formula (2Ae) are used, examples of the group represented by formula (2A) include groups represented by the following formulas (2Aa) to (2Ae). 21 , Y 22 , X b1 ~X b5 , R y , X 21 , and X 22 is as described above.

[0055] [ka]

[0056] * indicates the bond position.

[0057] In formula (1), A 1 As the group, a group represented by formula (1A) is preferred in that the effects of the present invention are more likely to be excellent.

[0058] In terms of achieving better effects of the present invention, it is preferable that the group represented by formula (1A) and the group represented by formula (2A) do not contain a fluorine atom. 1 Preferably, does not contain a fluorine atom.

[0059] In formula (1), D 1 represents a substituent having a nitrogen atom and an aromatic ring. The term "a substituent having an aromatic ring" means that the substituent has an aromatic ring in part or all of the substituent. The above-mentioned substituent having an aromatic ring also has a nitrogen atom. The nitrogen atom may be contained as a ring member atom of the aromatic ring, or may be contained at a position other than a ring member atom of the aromatic ring. D 1As the substituent, in terms of more excellent effects of the present invention, it is preferable that the substituent be a substituent having an aromatic ring containing a nitrogen atom as a ring member, or a substituent having a fused ring formed by condensing an aromatic ring with another ring containing a nitrogen atom, and it is more preferable that the substituent be a substituent having a fused ring formed by condensing an aromatic ring with another ring containing a nitrogen atom. Note that in the above-mentioned fused ring, the aromatic ring may be a nitrogen-containing aromatic ring.

[0060] D 1 The aromatic ring contained in may be either a monocyclic ring or a polycyclic ring. D 1 The number of ring members in the aromatic ring is not particularly limited, and is, for example, preferably 5 to 40, and more preferably 5 to 30. D 1 Examples of the aromatic ring contained in include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic hydrocarbon ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. The aromatic heterocycle is not particularly limited, and examples thereof include a thiophene ring, a furan ring, a pyran ring, a thiazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an oxazole ring, a selenophene ring, an imidazole ring, a quinoxaline ring, and a benzothiazole ring. Also, D 1 The substituent having an aromatic ring represented by the formula (I) may further contain another ring, and the aromatic ring and the other ring may be condensed to form a condensed ring. Examples of the other ring include alicyclic rings such as a cycloalkane ring, and alicyclic rings containing a nitrogen atom as a ring member atom such as a piperidine ring, a piperazine ring, an imidazolidine ring, etc. The alicyclic ring containing a nitrogen atom as a ring member atom is preferably 5- or 6-membered and preferably contains 1 to 3 nitrogen atoms. D 1 In terms of the effects of the present invention being more excellent, the substituent having an aromatic ring represented by the formula (I) is preferably a substituent having a fused ring formed by condensing an aromatic ring with an alicyclic ring containing a nitrogen atom as a ring member. In the fused ring, the aromatic ring may be a nitrogen-containing aromatic ring.

[0061] D 1 is preferably a group represented by either formula (1D) or formula (2D) described below. The group represented by (1D) will be explained below.

[0062] [ka]

[0063] In formula (1D), * represents the bonding position. Ar d11 represents an aromatic ring containing two or more carbon atoms, which may have a substituent. d11 represents an aromatic ring containing at least two carbon atoms (meaning the two carbon atoms specified in formula (1D)), which may have a substituent. Ar d11 As the ring, an aromatic heterocycle is preferable, and a quinoxaline ring or a pyrazine ring is more preferable. Ar d11 Examples of the substituent that the aromatic ring represented by the formula (I) has include the groups exemplified as the substituent W. An optionally substituted alkyl group, a halogen atom, or a cyano group is preferable, and an optionally substituted alkyl group or a chlorine atom is more preferable.

[0064] R d11 and R d12 each independently represents an aromatic ring group which may have a substituent or -C(R L11 )(R L12 )(R L13 ) The aromatic ring group includes an aryl group and a heteroaryl group, and among these, an aryl group is preferred, a phenyl group, a naphthyl group, or a fluorenyl group is more preferred, and a phenyl group or a naphthyl group is even more preferred. Furthermore, examples of the substituent that the aromatic ring group may have include the groups exemplified as the substituent W, and among these, an alkyl group (preferably having 1 to 3 carbon atoms) or a chlorine atom is preferred, and an alkyl group (preferably having 1 to 3 carbon atoms) is more preferred. In particular, when the aromatic ring group is a phenyl group, the phenyl group preferably has a substituent (in other words, the phenyl group preferably has a substituent). The number of substituents is preferably 1 to 5, and more preferably 1 to 3.

[0065] R L11 ~R L13 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. The alkyl group may be linear, branched, or cyclic. Examples of the aromatic ring group include an aryl group and a heteroaryl group. Of these, an aryl group is preferred, a phenyl group, a naphthyl group, or a fluorenyl group is more preferred, and a phenyl group or a naphthyl group is even more preferred. Examples of the substituent that the alkyl group and the aromatic ring group may have include the groups exemplified as the substituent W, and among these, an alkyl group (preferably having 1 to 3 carbon atoms) or a chlorine atom is preferred, and an alkyl group (preferably having 1 to 3 carbon atoms) is more preferred.

[0066] Also, R L11 ~R L13 may be bonded to each other to form a ring. L11 ~R L13 The optionally substituted alkyl group represented by the following formula (I) and the optionally substituted aromatic ring group (preferably an optionally substituted aryl group and an optionally substituted heteroaryl group) may be bonded to each other to form a ring. Below, R L11 ~R L13 are bonded to each other to form a ring.

[0067] For example, alkyl groups which may have substituents may be bonded to each other to form a ring. Substituents in an aryl group which may have substituents and alkyl groups which may have substituents may be bonded to each other to form a ring. Substituents in a heteroaryl group which may have substituents and alkyl groups which may have substituents may be bonded to each other to form a ring. Substituents in an aryl group which may have substituents and substituents in another aryl group which may have substituents may be bonded to each other to form a ring. Substituents in an aryl group which may have substituents and substituents in a heteroaryl group which may have substituents may be bonded to each other to form a ring. Substituents in a heteroaryl group which may have substituents and substituents in another heteroaryl group which may have substituents may be bonded to each other to form a ring. A substituent on the ring thus formed may be bonded to another alkyl group which may have a substituent, a substituent on another aryl group which may have a substituent, or a substituent on another heteroaryl group which may have a substituent to form a further ring. As described above, the group formed by bonding a substituent to another substituent (for example, a substituent in an aryl group which may have a substituent and a substituent in a heteroaryl group which may have a substituent) may be a single bond. In addition, R L11 ~R L13 When an optionally substituted alkyl group represented by the formula: and an optionally substituted aromatic ring group (preferably an optionally substituted aryl group or an optionally substituted heteroaryl group) are bonded to each other to form a ring, -C(R L11 )(R L12 )(R L13 ) is preferably other than an aryl group or a heteroaryl group.

[0068] R L11 ~R L13When they are bonded to each other to form a ring, the ring is preferably a monocyclic or polycyclic cycloalkane ring, in terms of achieving better effects of the present invention. Below, R L11 ~R L13 are bonded to each other to form a monocyclic or polycyclic cycloalkane ring. R L11 ~R L13 When they are bonded to each other to form a ring, R L11 and an alkyl group represented by R L12 and an alkyl group represented by R L11 and an alkyl group represented by R L12 and a substituent on a ring (for example, a monocyclic cycloalkane ring) formed by bonding together alkyl groups represented by R L13 and the alkyl groups represented by -C(R L11 )(R L12 )(R L13 ) may be a cycloalkyl group (preferably a cyclohexyl group) which may have a substituent. The cycloalkyl group preferably has 3 to 12 ring members, more preferably 3 to 8 ring members, and even more preferably 3 to 6 ring members. The cycloalkyl group may be monocyclic (eg, cyclohexyl group, etc.) or polycyclic (eg, 1-adamantyl group, etc.). The cycloalkyl group may have a substituent. Examples of the substituent include the groups exemplified as the substituent W, and among these, an alkyl group (preferably having 1 to 3 carbon atoms) is preferred. The substituents of the cycloalkyl group may be bonded to each other to form a ring, and the ring formed by bonding the substituents to each other may be other than a cycloalkane ring.

[0069] R d11 and R d12Among these, each of the groups independently is preferably an aromatic ring group which may have a substituent or an alkyl group which may have a substituent (examples of the alkyl group include linear and branched alkyl groups and cycloalkyl groups), and more preferably a group represented by formula (X) or an alkyl group which may have a substituent (examples of the alkyl group include linear and branched alkyl groups and cycloalkyl groups).

[0070] As the group represented by formula (X), a group represented by formula (Z) described later is preferred, and a group represented by formula (ZB) described later is more preferred.

[0071] Also, R d11 and R d12 In order to obtain a more excellent effect of the present invention, it is preferable that R have different structures. d11 and R d12 Among these, it is preferred that one of them represents a group represented by formula (X) (among which, a group represented by formula (ZB) described later is preferred), and the other represents an alkyl group which may have a substituent (examples of the alkyl group include linear and branched alkyl groups and cycloalkyl groups).

[0072] [ka]

[0073] In formula (X), * represents a bonding position. C 1 is R d1 It represents a monocyclic aromatic ring containing at least two carbon atoms (meaning the two carbon atoms clearly shown in formula (X)), which may have a substituent other than the above. Examples of the monocyclic aromatic ring include a monocyclic aromatic hydrocarbon ring and a monocyclic aromatic heterocycle. Examples of the aromatic hydrocarbon ring include a benzene ring. Examples of the aromatic heterocycle include a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a thiazole ring, a pyridine ring, and an oxazole ring. As the monocyclic aromatic ring, an aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred, in terms of achieving better effects of the present invention.

[0074] R d1 represents an alkyl group, a silyl group, an alkoxy group, an alkylthio group, a cyano group, a halogen atom, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group, and is preferably an alkyl group, a silyl group, an alkoxy group, an alkylthio group, a cyano group, a halogen atom, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group, and more preferably a halogen atom or an alkyl group. These groups may further have a substituent, if possible. In addition, R d1 Examples of the halogen atom represented by the formula (I) include a fluorine atom, an iodine atom, a bromine atom, and a chlorine atom, of which a fluorine atom or a chlorine atom is preferred, and a chlorine atom is more preferred.

[0075] R d1 and C 1 may be bonded to each other to form a non-aromatic ring. C 1 The aromatic ring of is directly bonded to the nitrogen atom specified in formula (1D).

[0076] [ka]

[0077] In formula (Z), T 1 ~T 4 are each independently -CR e12 = or nitrogen atom (=N-). e12 represents a hydrogen atom or a substituent.

[0078] T 1 ~T 4 At least one of the is -CR e12 = and R e12 Preferably, at least one of represents a substituent, and at least T 4 Ga-CR e12 = and T 4R in e12 More preferably, represents an alkyl group, an aryl group, or a heteroaryl group. R e12 Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W, and among these, an alkyl group, an aryl group, a heteroaryl group, a silyl group, a halogen atom, or a cyano group is preferred, and an alkyl group, an aryl group, a heteroaryl group, a silyl group, a halogen atom, or a cyano group is more preferred. These groups may further have a substituent. e12 The halogen atom represented by the formula (I) includes a fluorine atom, an iodine atom, a bromine atom, or a chlorine atom, and is preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom. R in formula (Z) e12 If there are multiple e12 They may be the same or different from each other.

[0079] R in formula (Z) f2 is R in formula (X) d1 The same definition and preferred embodiments are also the same. R f2 And, T 1 R in e12 may be bonded to each other to form a non-aromatic ring.

[0080] [ka]

[0081] In formula (ZB), T 1 ~T 3 are each independently -CR e12 = or nitrogen atom. R e12 represents a hydrogen atom or a substituent. R in formula (ZB) e12 is R in formula (Z) e12 The same definition and preferred embodiments are also the same.

[0082] In formula (ZB), R f3 and R f4Each of the groups independently represents an alkyl group, an aryl group, or a heteroaryl group. These groups may further have a substituent, if possible. * indicates the bond position.

[0083] In formula (1D), R d13 represents a hydrogen atom or a substituent. R d13 is preferably a hydrogen atom.

[0084] As the group represented by the above formula (1D), a group represented by the formula (3D) described later is preferred, a group represented by the formula (4D) described later is more preferred, and a group represented by the formula (5D) described later is even more preferred, in terms of better effects of the present invention. Below, formulas (3D) to (5D) will be explained one by one.

[0085] [ka]

[0086] In formula (3D), * and R d11 ~R d13 represents * and R in the above formula (1D). d11 ~R d13 The same definition and preferred embodiments are also the same. E d31 ~E d34 each independently represents a nitrogen atom or -CR E31 = R E31 represents a hydrogen atom or a substituent. In addition, R E31 If there are multiple E31 They may be bonded to each other to form a ring. E d31 ~E d34 At least two of the groups are preferably nitrogen atoms, and at least E d31 and E d34 is more preferably a nitrogen atom, and E d31 and E d34 It is more preferred that only nitrogen atoms are present. R E31The ring formed by bonding together is preferably an aromatic ring, more preferably a benzene ring or a pyridine ring. E31 The ring formed by bonding together may further have a substituent.

[0087] [ka]

[0088] In formula (4D), * and R d11 ~R d13 represents * and R in the above formula (1D). d11 ~R d13 The same definition and preferred embodiments are also the same. R d44 and R d45 each independently represents a hydrogen atom or a substituent. In addition, R d44 and R d45 may be bonded to each other to form a ring. d44 and R d45 The ring formed by bonding together is preferably an aromatic ring, more preferably a benzene ring or a pyridine ring, and even more preferably a benzene ring. d44 and R d45 The ring formed by bonding together may further have a substituent.

[0089] [ka]

[0090] In formula (5D), * and R d11 ~R d13 represents * and R in the above formula (1D). d11 ~R d13 The same definition and preferred embodiments are also the same. E d51 and E d52 each independently represents a nitrogen atom or -CR E51 = represents. R E51 represents a hydrogen atom or a substituent. R E51is preferably a hydrogen atom.

[0091] R d54 and R d55 each independently represents a hydrogen atom or a substituent. R d54 and R d55 Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W, and among these, a halogen atom or a cyano group is preferred, a fluorine atom, a chlorine atom or a cyano group is more preferred, and a chlorine atom is particularly preferred. In addition, R d54 and R d55 may be bonded to each other to form a ring. d54 and R d55 The ring formed by bonding together is preferably an aromatic ring, more preferably a benzene ring or a pyridine ring. d54 and R d55 The ring formed by bonding together may further have a substituent.

[0092] Next, the group represented by (2D) will be described.

[0093] [ka]

[0094] In formula (2D), * represents the bonding position. Ar d21 represents an aromatic ring containing two or more carbon atoms, which may have a substituent. d21 represents an aromatic ring containing at least two carbon atoms (meaning the two carbon atoms specified in formula (2D)), which may have a substituent. Ar d21 As the Ar in formula (1D), d21 The same definition and preferred embodiments are also the same. d21 Among these, a benzene ring or a naphthalene ring, which may have a substituent, is preferable.

[0095] R d22represents an aromatic ring group which may have a substituent or -C(R L21 )(R L22 )(R L23 ) represents R L21 ~R L23 Each of R independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. L21 ~R L23 may be bonded to each other to form a ring. R d22 As for R in formula (1D), d12 The meaning and preferred embodiments are also the same. L21 ~R L23 is R in formula (1D) d12 R in L11 ~R L13 and the preferred embodiments are also the same.

[0096] X d21 is a sulfur atom, an oxygen atom, or -C(R L24 )(R L25 )- represents. R L24 and R L25 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. The alkyl group may be linear, branched, or cyclic. Examples of the aromatic ring group include an aryl group and a heteroaryl group. Of these, an aryl group is preferred, a phenyl group, a naphthyl group, or a fluorenyl group is more preferred, and a phenyl group or a naphthyl group is even more preferred. Examples of the substituent that the alkyl group and the aromatic ring group may have include the groups exemplified as the substituent W, and among these, an alkyl group (preferably having 1 to 3 carbon atoms) or a chlorine atom is preferred, and an alkyl group (preferably having 1 to 3 carbon atoms) is more preferred.

[0097] In addition, R L24 and R L25 may be bonded to each other to form a ring. R L24 and RL25 The ring formed by bonding together is preferably a monocyclic or polycyclic cycloalkane ring. The number of ring members in the cycloalkyl ring is preferably 3 to 12, more preferably 3 to 8, and even more preferably 3 to 6. The cycloalkyl ring may have a substituent. Examples of the substituent include the groups exemplified as the substituent W, and among these, alkyl groups (preferably having 1 to 3 carbon atoms) are preferred.

[0098] R d23 represents a hydrogen atom or a substituent. R d23 is preferably a hydrogen atom.

[0099] As the group represented by the above formula (2D), a group represented by the below-mentioned formula (6D) is preferred in terms of achieving better effects of the present invention. Formula (6D) will be explained below.

[0100] [ka]

[0101] * and X in formula (6D) d21 , R d22 , and R d23 is * in formula (2D), X d21 , R d22 , and R d23 The same definition and preferred embodiments are also the same. R d61 ~R d64 each independently represents a hydrogen atom or a substituent. R d61 ~R d64 Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W, and a halogen atom or a cyano group is preferred, a fluorine atom, a chlorine atom or a cyano group is more preferred, and a chlorine atom is particularly preferred. Also, R d61 ~R d64 may be bonded to each other to form a ring (R d61 and R d62 , R d62and R d63 , and / or R d63 and R d64 However, they are preferably bonded together to form a ring. d61 ~R d64 The ring formed by bonding together is preferably an aromatic ring, more preferably a benzene ring or a pyridine ring. d61 ~R d64 The ring formed by bonding together may further have a substituent.

[0102] In terms of achieving better effects of the present invention, it is preferable that formula (6D) satisfy at least one of the following requirements. Requirement X1:R d22 represents an aromatic ring group which may have a substituent. Requirement X2:X d21 -C(R L24 )(R L25 )- and R L24 and R L25 and are bonded to each other to form a ring. Requirement X3:R d61 and R d62 , R d62 and R d63 , and R d63 and R d64 Any one or more of the following may be bonded to each other to form a ring.

[0103] In terms of achieving better effects of the present invention, it is preferable that the group represented by formula (1D) and the group represented by formula (2D) do not contain a fluorine atom. 1 Preferably, does not contain a fluorine atom.

[0104] In formula (1), R 1 represents a hydrogen atom or a substituent. R 1 is preferably a hydrogen atom.

[0105] Specific examples of the specific compound are shown below, but the specific compound of the present invention is not limited to these. In addition, "R" in the structural formula of the compound shown below represents any one selected from the groups shown in the "R group" described below. The * shown in the group shown in the "R group" represents the bonding position. In addition, "R" in the structural formula of the compound shown below represents A in the above formula (1). 1 This corresponds to the group represented by the formula:

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] 《R group》

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] The molecular weight of the specific compound is preferably 350 or more, more preferably 400 or more, and even more preferably 500 or more. The upper limit is preferably 1200 or less, more preferably 1000 or less, and even more preferably 900 or less. If the molecular weight is 1200 or less, the deposition temperature does not become high and decomposition of the compound is unlikely to occur. If the molecular weight is 350 or more, the glass transition point of the deposited film does not decrease and the heat resistance of the photoelectric conversion element is improved.

[0118] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, an optical sensor, or a photovoltaic cell. The specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.

[0119] The maximum absorption wavelength of the specific compound is, for example, preferably in the range of 300 to 700 nm, and more preferably in the range of 400 to 600 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1. However, if the specific compound is not soluble in chloroform, the specific compound is vapor-deposited and the value measured using the specific compound in a film state is regarded as the maximum absorption wavelength of the specific compound.

[0120] The maximum absorption wavelength of the photoelectric conversion film is, for example, preferably in the range of 300 to 700 nm, and more preferably in the range of 400 to 700 nm.

[0121] The specific compound can also be used as a dye, a p-type semiconductor material (a material with excellent hole transport properties), and an n-type semiconductor material (a material with excellent electron transport properties).

[0122] When using a specific compound as a p-type semiconductor material, the ionization potential of the specific compound is preferably 5.0 to 6.0 eV.

[0123] When using a specific compound as an n-type semiconductor material, the electron affinity of the specific compound is preferably 3.0 to 4.5 eV. In this specification, as the value of the electron affinity, the value of the reciprocal of the LUMO value (the value multiplied by minus 1) obtained by the B3LYP / 6-31G(d) calculation using Gaussian '09 (software, manufactured by Gaussian) is used.

[0124] From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the specific compound in the photoelectric conversion film (= film thickness in terms of a single layer of the specific compound / film thickness of the photoelectric conversion film × 100) is preferably 15 to 85% by volume. The photoelectric conversion element may contain one kind of the specific compound alone or may contain two or more kinds.

[0125] <n-type semiconductor material> The photoelectric conversion film preferably contains an n-type semiconductor material in addition to the specific compound. The n-type semiconductor material is an acceptor-type organic semiconductor material (compound), which refers to an organic compound having a property of easily accepting electrons. More specifically, the n-type semiconductor material is preferably an organic compound having a larger electron affinity than the specific compound when used in contact with the above-mentioned specific compound. Also, the n-type semiconductor material is preferably an organic compound having a larger electron affinity than the dye when used in contact with the dye described later. The electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV. 9]

[0126] Examples of n-type semiconductor materials include fullerenes selected from the group consisting of fullerenes and derivatives thereof, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, and pyrazole). , imidazole, and thiazole); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives, oxadiazole 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; and the compounds described in paragraphs

[0056] and

[0057] of JP 2006-100767 A.

[0127] Preferably, the n-type semiconductor material comprises fullerenes selected from the group consisting of fullerenes and derivatives thereof. Examples of fullerenes include fullerene C60, fullerene C70, fullerene C76, fullerene C78, ​​fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene C540, and mixed fullerenes. Examples of fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerene. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. Preferred fullerene derivatives include the compounds described in JP-A-2007-123707.

[0128] When the photoelectric conversion film contains an n-type semiconductor material, the content of the n-type semiconductor material in the photoelectric conversion film (= film thickness in terms of a single layer of the n-type semiconductor material / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and still more preferably 25 to 50% by volume. The n-type semiconductor material may be used alone or in combination of two or more.

[0129] When the n-type semiconductor material contains fullerenes, the content of fullerenes relative to the total content of the n-type semiconductor material (= (film thickness in terms of a single layer of fullerenes / total film thickness of each n-type semiconductor material in terms of a single layer) × 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. The fullerenes may be used alone or in combination of two or more.

[0130] The molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.

[0131] <p-type semiconductor material> In addition to the specific compound, it is also preferable that the photoelectric conversion film contains a p-type semiconductor material. The p-type semiconductor material is a donor-type organic semiconductor material (compound), which refers to an organic compound having a property of easily donating electrons. Specifically, the p-type semiconductor material is preferably an organic compound having better hole transport properties than the specific compound in the photoelectric conversion film, and more preferably an organic compound having better hole transport properties than both the specific compound and the dye described below. In this specification, the hole transport property (hole carrier mobility) of a compound can be evaluated, for example, by the Time-of-Flight method (for example, the flying range time method and the TOF method, etc.) or using a field effect transistor element. The hole carrier mobility of the p-type semiconductor material is -4 cm 2 / V·s or more is preferable, -3 cm 2 [[ID=三十二]] / V·s or more is more preferable, -2 cm 2The upper limit is 10 cm / V·s to prevent a small amount of current from flowing when no light is irradiated. 2 / V·s or less is preferable. The p-type semiconductor material preferably has a smaller ionization potential than the specific compound in the photoelectric conversion film, and more preferably has a smaller ionization potential than both the specific compound and the dye described below.

[0132] Examples of p-type semiconductor materials include triarylamine compounds (e.g., 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 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), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (e.g., thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b]thiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of JP 2018-14474 A, compounds described in paragraphs

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

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

[0015] to

[0025] of WO2018-207722; compounds described in paragraphs

[0045] to

[0053] of JP2019-54228; 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 JP2019-80052; Examples of suitable compounds include compounds described in paragraphs

[0044] to

[0054] of International Patent Publication WO2019-054125 and in paragraphs

[0041] to

[0046] of WO2019-093188, 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.

[0133] The p-type semiconductor material is also preferably a compound represented by any one of formulas (p1) to (p6), and more preferably a compound represented by formula (p1).

[0134] [ka]

[0135] In formulae (p1) to (p6), two Rs each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylthio group, a (hetero)arylthio group, an alkylamino group, a (hetero)arylamino group, and a (hetero)aryl group. The substituent may further have a substituent. Specifically, the (hetero)aryl group may be an arylaryl group (biaryl group) which may further have a substituent. At least one of the two aryl groups constituting the biaryl group may be a heteroaryl group. The term "(hetero)aryl group" is a concept that includes both an aryl group and a heteroaryl group. Specifically, a "(hetero)arylthio group" may be either an arylthio group or a heteroarylthio group. Furthermore, as R, a group represented by R in formula (IX) described in WO2019-081416 is also preferred.

[0136] X and Y each independently represent -CR 2 2-, sulfur atom (-S-), oxygen atom (-O-), -NR 2 -or-SiR 2 Represents 2-. R 2 represents a hydrogen atom, an alkyl group which may have a substituent (preferably a methyl group or a trifluoromethyl group), an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. 2 may be the same or different. Ar represents an aromatic ring group, and is preferably a benzene ring group. The aromatic ring group may be either monocyclic or polycyclic (for example, bicyclic, tricyclic, or tetracyclic).

[0137] When the photoelectric conversion film contains a p-type semiconductor material, the content of the p-type semiconductor material in the photoelectric conversion film (=film thickness of the p-type semiconductor material in terms of a single layer / 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 25 to 50% by volume. The p-type semiconductor materials may be used singly or in combination of two or more.

[0138] <Dye> The photoelectric conversion film may contain a dye in addition to the specific compound. The dye is preferably an organic dye. Examples of the dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, and fulgide dyes. dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, quinoxaline dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, and those described in paragraphs

[0083] to

[0089] of JP 2014-082483 A the compounds described in paragraphs

[0029] to

[0033] of JP 2009-167348 A, the compounds described in paragraphs

[0197] to

[0227] of JP 2012-077064 A, the compounds described in paragraphs

[0035] to

[0038] of WO 2018-105269 A, the compounds described in paragraphs

[0041] to

[0043] of WO 2018-186389 A, the compounds described in paragraphs

[0059] to

[0062] of WO 2018-186397 A, Examples include the compounds described in paragraphs

[0078] to

[0083] of WO2019-009249, the compounds described in paragraphs

[0054] to

[0056] of WO2019-049946, the compounds described in paragraphs

[0059] to

[0063] of WO2019-054327, the compounds described in paragraphs

[0086] to

[0087] of WO2019-098161, and the compounds described in paragraphs

[0085] to

[0114] of WO2020-013246.

[0139] The content of the dye in the photoelectric conversion film (=thickness of dye in single layer equivalent / thickness of photoelectric conversion film×100) is preferably 1 to 85% by volume, more preferably 5 to 60% by volume, and even more preferably 10 to 40% by volume. The content of the dye in the photoelectric conversion film relative to the total content of the specific compound and the dye (=(film thickness of the dye in monolayer equivalent / (film thickness of the specific compound in monolayer equivalent+film thickness of the dye in monolayer equivalent)×100) is preferably 1 to 75 volume %, more preferably 5 to 65 volume %, and even more preferably 10 to 60 volume %. The dyes may be used alone or in combination of two or more.

[0140] The maximum absorption wavelength of the dye is, for example, preferably in the range of 400 to 700 nm, and more preferably in the range of 400 to 650 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the dye's absorption spectrum to a concentration such that the absorbance is 0.5 to 1. However, if the dye is not soluble in chloroform, the dye is evaporated and the value measured using the dye in a film state is taken as the maximum absorption wavelength of the dye.

[0141] It is also preferable that the photoelectric conversion film is substantially composed of only a specific compound, an n-type semiconductor material, and a p-type semiconductor material. "The photoelectric conversion film is substantially composed of only a specific compound, an n-type semiconductor material, and a p-type semiconductor material" means that the total content of the specific compound, the n-type semiconductor material, and the p-type semiconductor material is 95 to 100 mass% with respect to the total mass of the photoelectric conversion film.

[0142] It is also preferable that the photoelectric conversion film is substantially composed of only the specific compound, dye, n-type semiconductor material, and p-type semiconductor material. "The photoelectric conversion film is substantially composed of only the specific compound, dye, n-type semiconductor material, and p-type semiconductor material" means that the total content of the specific compound, n-type semiconductor material, p-type semiconductor material, and dye is 95 to 100 mass% with respect to the total mass of the photoelectric conversion film.

[0143] Furthermore, when the photoelectric conversion film contains an n-type semiconductor material and / or a p-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state in which a specific compound is mixed with an n-type semiconductor material and / or a p-type semiconductor material. When the photoelectric conversion film contains a dye and an n-type semiconductor material and / or a p-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state in which a specific compound, the dye, and the n-type semiconductor material and / or the p-type semiconductor material are mixed. A mixed layer is a layer in which two or more materials are mixed within a single layer.

[0144] The photoelectric conversion film containing the specific compound is a non-luminescent film and has properties 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, and more preferably 0.1% or less.

[0145] <Film formation method> As a method for forming the photoelectric conversion film, for example, a dry film formation method can be mentioned. Examples of dry film formation methods include vapor deposition (e.g., vacuum deposition), sputtering, physical vapor deposition such as ion plating and molecular beam epitaxy (MBE), and chemical vapor deposition (CVD) such as plasma polymerization, with vacuum deposition being preferred. When forming the photoelectric conversion film by vacuum deposition, the manufacturing conditions, such as the degree of vacuum and deposition temperature, can be set according to conventional methods.

[0146] The thickness of the photoelectric conversion film is preferably from 10 to 1000 nm, more preferably from 50 to 800 nm, still more preferably from 50 to 500 nm, and particularly preferably from 50 to 400 nm.

[0147] [Electrode (conductive film)] The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident through the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, or 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; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes. Of these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0148] Typically, when a conductive film is made thinner than a certain range, the resistance value increases sharply. However, in a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance may be, for example, 100 to 10,000 Ω / □, allowing for a wide range of film thicknesses. Furthermore, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher its light transmittance. Increased 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 thinning, the film thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0149] Depending on the application, the lower electrode 11 may be made transparent or non-transparent and light-reflective. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO or FTO), 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, and 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 graphene and carbon nanotubes.

[0150] The method for forming the electrodes can be appropriately selected depending on the electrode material, and 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 of methods include an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (for example, a sol-gel method), and coating of a dispersion of indium tin oxide.

[0151] [Charge blocking film: electron blocking film, hole blocking film] The photoelectric conversion element of the present invention preferably has one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film. The intermediate layer may be, for example, a charge-blocking film. When the photoelectric conversion element has the film, the resulting photoelectric conversion element has better properties (e.g., photoelectric conversion efficiency, responsiveness, etc.). The charge-blocking film may be, for example, an electron-blocking film or a hole-blocking film. Each of these films will be described in detail below.

[0152] <Electron blocking film> The electron blocking film is a donor organic semiconductor material (compound). The donor organic semiconductor material may also be the p-type organic semiconductor. The p-type organic semiconductor may be used alone or in combination of two or more.

[0153] Furthermore, examples of p-type organic semiconductors used in electron blocking films include compounds with a smaller ionization potential than n-type semiconductor materials, and if this condition is met, the above-mentioned dyes can also be used.

[0154] Furthermore, polymeric materials can also be used as the electron blocking film. Examples of polymeric materials include polymers of phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.

[0155] The electron blocking film may be composed of multiple films. The electron blocking film may be composed of an inorganic material. Generally, 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 photoelectric conversion 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.

[0156] <Hole-blocking film> The hole-blocking film is an acceptor organic semiconductor material (compound). As the acceptor organic semiconductor material, the above-mentioned n-type semiconductor material can also be used.

[0157] The charge blocking film can be produced by, for example, a dry film-forming method or a wet film-forming method. 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. 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 from the standpoint of high-precision patterning.

[0158] 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.

[0159] 〔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. In the photoelectric conversion element, the position of the substrate is not particularly limited, and typically, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated in this order on the substrate.

[0160] [Sealing layer] The photoelectric conversion element may further include a sealing layer. The performance of photoelectric conversion materials can be significantly degraded by the presence of degrading factors such as water molecules, etc. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer such as a dense ceramic such as metal oxide, metal nitride, or metal nitride oxide, which does not allow water molecules to penetrate, or a sealing layer such as diamond-like carbon (DLC). The sealing layer may be made of a material selected and produced in accordance with the description in paragraphs

[0210] to

[0215] of JP-A-2011-082508.

[0161] [Image sensor, optical sensor] Photoelectric conversion elements are used, for example, as imaging elements. An imaging element is an element that converts the optical information of an image into an electrical signal, and is usually composed of 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. To this end, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The imaging device is mounted on an imaging device of a digital camera, a digital video camera, an electronic endoscope, an imaging module of a mobile phone, or the like.

[0162] The photoelectric conversion element of the present invention is also preferably used in an optical sensor having the photoelectric conversion element of the present invention. The optical sensor may be the photoelectric conversion element alone, or may be a line sensor in which the photoelectric conversion elements are arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion elements are arranged in a plane.

[0163] [Compound] The present invention also relates to compounds. The compound of the present invention has the same meaning as the specific compound described above, and the preferred embodiments are also the same. [Example]

[0164] 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.

[0165] [Compound (evaluation compound)] [Method for synthesizing compounds (2-24) and (2-25)]

[0166] [ka]

[0167] <Synthesis of Compound (2-24) and Compound (2-25)> 5 mmol of compound (2-24-1), 6.0 mmol of a mixture of compound (2-24-2) and compound (2-24-3), and 30 mL of acetic anhydride were added to a glass reaction vessel and reacted at 110°C for 3 hours under a nitrogen atmosphere. Methanol was added to the reaction solution, and the solid was collected by filtration. The obtained solid was washed with THF (tetrahydrofuran) and toluene, and compound (2-24) and compound (2-25) were separated by silica gel column chromatography. Each was purified by sublimation to obtain 2.5 mmol of compound (2-24) and 1.0 mmol of compound (2-25). Compound (2-24): 1 H-NMR(CDCl3,400MHz)δ=1.35(2H,s),1.65(2H,s),2.09(6H,s),3.76(1H,s),7.07(1H,d),7.37(2H,d ),7.50(1H,t),7.59-7.68(2H,m),7.71(1H,d),7.82(1H,s),7.88(1H,dd),8.08(1H,d),9.11(1H,d). Compound (2-25): 1 H-NMR(CDCl3,400MHz)δ=1.35(2H,s),1.66(2H,s),2.09(6H,s),3.75(1H,s),7.04(1H,d),7.2 0(1H,d),7.38(2H,d),7.50(1H,t),7.59-7.68(3H,m),7.88(1H,d),8.08(1H,d),9.10(1H,d).

[0168] Other specific compounds were also synthesized with reference to the above synthesis methods. The specific compounds used in the test and the comparative compounds are shown below. In the following, compounds (1-1) to (1-10) and compounds (2-1) to (2-32) are specific compounds. Hereinafter, the specific compound and the comparative compound will be collectively referred to as the evaluation compound. The evaluation compound was used to prepare a photoelectric conversion element as described below.

[0169] (Specific compound)

[0170] [ka] JPEG0007786971000029.jpg85163

[0171] [ka]

[0172] (Comparative Compound)

[0173] [ka]

[0174] [p-type semiconductor] The p-type semiconductors shown below were used as p-type semiconductors for evaluation in the production of photoelectric conversion elements, which will be described later.

[0175] [ka]

[0176] [n-type semiconductor] Fullerene C 60 (C60) was used as an n-type semiconductor for evaluation in the production of a photoelectric conversion element, which will be described later.

[0177] [Pigment] In the production of a photoelectric conversion element (B) described below, the dyes shown below were used as dyes for evaluation.

[0178] [ka]

[0179] [ka]

[0180] [evaluation] [Fabrication of photoelectric conversion element (A)] A photoelectric conversion element having the configuration shown in Fig. 2 was fabricated using an evaluation compound (specific compound or comparative compound). Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a film of the lower electrode 11 (thickness: 30 nm), and the following compound (B-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Furthermore, the materials shown in Table 1 (evaluation compound, p-type semiconductor, and n-type semiconductor (fullerene (C 60 )) was deposited at the rate ratio shown in Table 1 to form a photoelectric conversion film 12 having a bulk heterostructure. Furthermore, the following compound (B-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). An SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, and then an aluminum oxide (Al2O3) layer was formed on top of it by ALCVD (Atomic Layer Chemical Vapor Deposition), to produce a photoelectric conversion element.

[0181] [ka]

[0182] [Evaluation of photoelectric conversion element (A)] <Evaluation of photoelectric conversion efficiency> The operation of each photoelectric conversion element of the example and comparative example was confirmed. 2.0 × 10 for each photoelectric conversion element 5A voltage was applied to achieve an electric field strength of 1000 V / cm, and light was irradiated from the upper electrode (transparent conductive film) side to measure the integrated value of the photoelectric conversion efficiency (external quantum efficiency) in the wavelength range of 450 to 650 nm ("integrated value of the photoelectric conversion efficiency before annealing"). After that, the device was heated at 150°C for 30 minutes in a glove box, and then the integrated value of the photoelectric conversion efficiency (external quantum efficiency) in the wavelength range of 450 to 650 nm ("integrated value of the photoelectric conversion efficiency after annealing") was measured again in the same manner as above. Based on the obtained measurement values, the following evaluations (Evaluation 1 and Evaluation 2) were carried out.

[0183] (Evaluation 1: Photoelectric conversion efficiency after annealing) The relative photoelectric conversion efficiency was calculated by the following formula (S1), and evaluation was performed based on the following evaluation criteria. The results are shown in Table 1. Formula (S1): Relative photoelectric conversion efficiency = (integral value of photoelectric conversion efficiency in the wavelength range of 450 to 650 nm of each photoelectric conversion element of Examples or Comparative Examples after annealing) / (integral value of photoelectric conversion efficiency in the wavelength range of 450 to 650 nm of the photoelectric conversion element of Example 1-1 after annealing) Evaluation Criteria "AA": Photoelectric conversion efficiency fluctuation value is 1.5 or more "A": Relative photoelectric conversion efficiency is 1.3 or more and less than 1.5 "B": Relative photoelectric conversion efficiency is 1.1 or more and less than 1.3 "C": Relative photoelectric conversion efficiency is 0.9 or more and less than 1.1 "D": Relative photoelectric conversion efficiency is 0.7 or more and less than 0.9 "E": Relative photoelectric conversion efficiency less than 0.7

[0184] (Evaluation 2: Changes in photoelectric conversion efficiency due to annealing) The fluctuation value of the photoelectric conversion efficiency was calculated by the following formula (S2), and evaluation was carried out based on the following evaluation criteria. The results are shown in Table 1. Formula (S2): Fluctuation in photoelectric conversion efficiency = (integral value of photoelectric conversion efficiency in the wavelength range of 450 to 650 nm of each photoelectric conversion element of the Examples or Comparative Examples after annealing) / (integral value of photoelectric conversion efficiency in the wavelength range of 450 to 650 nm of each photoelectric conversion element of the Examples or Comparative Examples before annealing) Evaluation Criteria "A": The fluctuation value of photoelectric conversion efficiency is 1.1 or more "B": The fluctuation value of photoelectric conversion efficiency is 1.0 or more and less than 1.1 "C": The fluctuation value of photoelectric conversion efficiency is 0.9 or more and less than 1.0 "D": The fluctuation value of photoelectric conversion efficiency is 0.6 or more and less than 0.9 "E": The fluctuation value of photoelectric conversion efficiency is less than 0.6

[0185] <Evaluation of responsiveness> The response was evaluated using each of the photoelectric conversion elements of the example and comparative example.

[0186] (Rating 3: Response speed) 2.0 × 10 for each photoelectric conversion element 5 A voltage was applied to achieve an intensity of 1000 V / cm. An LED (light-emitting diode) was then momentarily turned on to irradiate the upper electrode (transparent conductive film) with light, and the resulting photocurrent was measured with an oscilloscope. The current intensity (signal intensity) before light irradiation was defined as 0%, and the maximum signal intensity measured upon light irradiation was defined as 100%. The time (rise time) required for the signal intensity to increase from 0% to 97% after light irradiation was calculated for each photoelectric conversion element. The relative response speed was then calculated using the following formula (S3), and evaluation was performed based on the following criteria. The results are shown in Table 1.

[0187] Formula (S3): Relative response speed=(rise time of each photoelectric conversion element of the example and comparative example) / (rise time of the photoelectric conversion element of Example 1-1) Evaluation Criteria "A": Relative response speed is less than 0.5 "B": Relative response speed is 0.5 or more and less than 1.0 "C": Relative response speed is 1.0 or more and less than 1.5 "D": Relative response speed is 1.5 or more and less than 2.0 "E": Relative response speed is 2.0 or higher

[0188] (Evaluation 4: Evaluation of response speed dependence on electric field strength) 7.5 × 10 for each photoelectric conversion element 4 A voltage was applied to achieve an intensity of 1000 V / cm. The LED was then momentarily turned on, and light was irradiated from the upper electrode (transparent conductive film) side. The photocurrent at this time was measured with an oscilloscope. The current intensity (signal intensity) before light irradiation was set to 0%, and the maximum signal intensity measured upon light irradiation was set to 100%. The time (rise time) required for the signal intensity to increase from 0% to 97% after light irradiation was calculated for each photoelectric conversion element. The dependence of the response speed on electric field intensity was then calculated using the following formula (S4), and evaluation was performed based on the following evaluation criteria. The denominator in formula (S4) was calculated according to the procedure in Evaluation 3 above. The results are shown in Table 1.

[0189] Equation (S4): Dependence of relative response speed on electric field strength = (7.5 x 10 4 The rise time of each photoelectric conversion element of the example or comparative example when a voltage is applied so that the intensity is 1.0 V / cm) / (2.0 × 10 5 V / cm) Evaluation Criteria "A": The field strength dependence of the relative response is less than 2.0 "B": The field strength dependence of the relative response is 2.0 or more and less than 3.0 "C": The field strength dependence of the relative response is 3.0 or more and less than 4.0 "D": The field strength dependence of the relative response is 4.0 or more and less than 5.0 "E": The field strength dependence of the relative response is 5.0 or more

[0190] Table 1 is shown below. In addition, in Tables 1 and 2, "D 1The structure of a specific compound is 1 The structure of the specific compound is shown. 1 represents a group represented by the above formula (1D), "1D"; 1 represents a group represented by the above formula (2D), "2D"; 1 When represents a group that does not fall into either of the above formulas (1D) and (2D), it is represented as "N". In addition, in Table 1 and Table 2, "A 1 The structure of a specific compound is 1 The structure of a specific compound is shown. 1 represents a group represented by the above formula (1A), "1A"; A in a specific compound 1 When represents a group represented by the above formula (2A), it is represented as "2A". In addition, in Tables 1 and 2, "Y" in the remarks column 11 / Y 12 and Y 21 / Y 22 The combination of A in a specific compound 1 represents a group represented by the above formula (1A), "Y 11 and Y 12 "Combination with" is shown, and A in a specific compound 1 represents a group represented by the above formula (2A), "Y 21 and Y 22 "O atom" means oxygen atom, "S atom" means sulfur atom, and "CN*" means =C(CN)2. In addition, in Tables 1 and 2, "R d11 / R d12 The asymmetry of D in a particular compound 1 represents a group represented by the above formula (1D), R d11 and R d12 indicates whether or not the R d11 and R d12 If they are not identical, it is indicated by "P", and if they are identical, it is indicated by "N". Also, "-" indicates that D in a particular compound 1 does not correspond to the group represented by the above formula (1D). In addition, in Tables 1 and 2, "X" in the remarks column d21 / R d22 The structure of a specific compound is 1 represents a group represented by the above formula (6D), it indicates whether or not at least one of the above requirements X1 to X3 is satisfied. If at least one of the above requirements X1 to X3 is satisfied, it is indicated by "P", and if not, it is indicated by "N". In addition, "-" indicates that D in a specific compound 1 does not correspond to the group represented by the above formula (6D). In addition, in Tables 1 and 2, "D 1 or A 1 The presence or absence of F atoms in a particular compound 1 and A 1 If not, it is indicated by "P", and if it is, it is indicated by "N". In addition, in Table 1 and Table 2, "A 1 The type of A in a specific compound 1 is a group represented by the above formula (1Aa), and X 11 Ga-CR x = represents X 12 represents a sulfur atom (provided that R x ), Y 11 represents an oxygen atom, and Y 12 represents =C(CN)2, and is indicated by "P" if applicable and "N" if not.

[0191] [Table 1]

[0192] [Table 2]

[0193] From the results in Table 1, it is clear that the photoelectric conversion elements of the examples have high photoelectric conversion efficiency in the visible light region (particularly in the wavelength region of 450 to 650 nm) even after heat treatment (annealing treatment).It is also clear that the photoelectric conversion elements of the examples are excellent in terms of fluctuations in photoelectric conversion efficiency due to heat treatment (annealing treatment), response speed, and suppression of the dependence of response speed on electric field strength.

[0194] In addition, from the comparison of the examples, D in a specific compound 1 It was confirmed that when represents a group represented by formula (1D), the fluctuation of photoelectric conversion efficiency due to heat treatment (annealing treatment) and the electric field strength dependency of response speed are more effectively suppressed.

[0195] In addition, from a comparison of examples (see Examples 1-1 to 1-10), D in a specific compound 1 represents a group represented by formula (2D), D 1 represents a group represented by formula (6D) and satisfies at least one of the above-mentioned requirements X1 to X3, it has been confirmed that the photoelectric conversion efficiency due to heat treatment (annealing treatment), the fluctuation of the photoelectric conversion efficiency due to heat treatment (annealing treatment), the response speed, and the suppression of the electric field strength dependency of the response speed are more excellent.

[0196] In addition, from the comparison of the examples (see Examples 1-12 to 1-43), D in the specific compound 1 represents a group represented by formula (1D), A 1 Y in formula (1A) 11 and Y 12 One of these represents an oxygen atom and the other represents =C(CN)2, or A 2 Y in formula (2A) 21 and Y 22 It was confirmed that when one of the groups represents an oxygen atom and the other represents =C(CN)2, the photoelectric conversion efficiency and response speed are improved by heat treatment (annealing treatment).

[0197] In addition, from the comparison of the examples (see Examples 1-12 to 1-43), D in the specific compound 1 represents a group represented by formula (1D), R in formula (1D)d11 and R d12 It was confirmed that when the structures of the layers are different from each other, the photoelectric conversion efficiency in the visible light region (particularly in the wavelength region of 450 to 650 nm) is higher even after heat treatment (annealing treatment).

[0198] In addition, from the comparison of the examples (see Examples 1-12 to 1-43), D in the specific compound 1 and A 1 However, it was confirmed that the response speed was superior when no fluorine atoms were present.

[0199] In addition, from a comparison of examples (see Examples 1-1 to 1-43), A in the specific compound 1 is a group represented by the above formula (1Aa), and X 11 Ga-CR x = represents X 12 represents a sulfur atom (provided that R x ), Y 11 represents an oxygen atom, and Y 12 When represents =C(CN)2 (specifically, A in a specific compound 1 represents a group represented by the above formula (1Aa-1), it was confirmed that the photoelectric conversion efficiency in the visible light region (particularly in the wavelength region of 450 to 650 nm) was superior even after heat treatment (annealing treatment).

[0200] Furthermore, from a comparison of examples (see Examples 1-29 to 1-30), D 1 is a group represented by formula (1D), R d11 and R d12 When one of the groups represents an alkyl group which may have a substituent (examples of the alkyl group include linear and branched alkyl groups and cycloalkyl groups), and the other represents a group represented by the above formula (X), it has been confirmed that the photoelectric conversion efficiency in the visible light region (particularly, the wavelength region of 450 to 650 nm) is superior even after heat treatment (annealing treatment). Furthermore, from a comparison of examples (see Examples 1-30 to 1-31), D 1is a group represented by formula (1D), R d11 and R d12 When one of the groups represents an alkyl group which may have a substituent (examples of the alkyl group include linear and branched alkyl groups and cycloalkyl groups), and the other represents a group represented by the above formula (ZB), it has been confirmed that the photoelectric conversion efficiency in the visible light region (particularly, the wavelength region of 450 to 650 nm) is superior even after heat treatment (annealing treatment), and the response speed is also superior.

[0201] [Fabrication of photoelectric conversion element (B)] The materials shown in Table 2 (evaluation compounds, n-type semiconductors (fullerene (C 60 )), a p-type semiconductor, and a dye) were deposited at a rate ratio shown in Table 2 to form a photoelectric conversion film 12 having a bulk heterostructure. A photoelectric conversion element was fabricated in the same manner as in the above-mentioned [Fabrication of photoelectric conversion element (A)].

[0202] [Evaluation of photoelectric conversion element (B)] The photoelectric conversion element (B) was evaluated in the same manner as in [Evaluation of photoelectric conversion element (A)]. The results are shown in Table 2. However, in the evaluation of photoelectric conversion element (B), formula (S1) for evaluation 1 and formula (S3) for evaluation 3 were calculated based on the following formulas. Formula (S1): Relative photoelectric conversion efficiency = (integral value of photoelectric conversion efficiency in the wavelength range of 450 to 650 nm of each photoelectric conversion element of the Examples or Comparative Examples after annealing) / (integral value of photoelectric conversion efficiency in the wavelength range of 450 to 650 nm of the photoelectric conversion element of Example 2-1 after annealing) Formula (S3): Relative response speed=(rise time of each photoelectric conversion element of the example and comparative example) / (rise time of the photoelectric conversion element of Example 2-1)

[0203] [Table 3]

[0204] [Table 4]

[0205] From the results in Table 2, it is clear that the photoelectric conversion elements of the examples have high photoelectric conversion efficiency in the visible light region (particularly in the wavelength region of 450 to 650 nm) even after heat treatment (annealing treatment).It is also clear that the photoelectric conversion elements of the examples are excellent in terms of fluctuations in photoelectric conversion efficiency due to heat treatment (annealing treatment), response speed, and suppression of the dependence of response speed on electric field strength.

[0206] In addition, from the comparison of the examples, D in a specific compound 1 It was confirmed that when represents a group represented by formula (1D), the fluctuation of photoelectric conversion efficiency due to heat treatment (annealing treatment) and the electric field strength dependency of response speed are more effectively suppressed.

[0207] In addition, from a comparison of examples (see Examples 2-23 to 2-54), D in a specific compound 1 represents a group represented by formula (1D), A 1 Y in formula (1A) 11 and Y 12 One of these represents an oxygen atom and the other represents =C(CN)2, or A 2 Y in formula (2A) 21 and Y 22 It was confirmed that when one of the groups represents an oxygen atom and the other represents =C(CN)2, the photoelectric conversion efficiency and response speed are improved by heat treatment (annealing treatment).

[0208] In addition, from a comparison of examples (see Examples 2-23 to 2-54), D in a specific compound 1 represents a group represented by formula (1D), R in formula (1D) d11 and R d12 It was confirmed that when the structures of the layers are different from each other, the photoelectric conversion efficiency in the visible light region (particularly in the wavelength region of 450 to 650 nm) is higher even after heat treatment (annealing treatment).

[0209] In addition, from a comparison of examples (see Examples 2-23 to 2-54), D in a specific compound1 and A 1 However, it was confirmed that the response speed was superior when no fluorine atoms were present.

[0210] Furthermore, from a comparison of examples (see Examples 2-41 and 2-42), D 1 is a group represented by formula (1D), R d11 and R d12 It has been confirmed that the response speed is superior when one of the groups represents an alkyl group which may have a substituent (examples of the alkyl group include linear and branched alkyl groups and cycloalkyl groups), and the other represents a group represented by the above formula (ZB). [Explanation of symbols]

[0211] 10a, 10b Photoelectric conversion element 11 Conductive film (bottom 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, The photoelectric conversion element, wherein the photoelectric conversion film contains at least one compound selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (1-10): 【Chemistry 1】 【change】 【change】 【change】 In formula (1), A １ represents a group represented by any one of formula (1Aa), formula (2Aa), formula (2Ab), and formula (2Ac). In formula (1), D １ represents a group represented by either formula (5D) or formula (6D). In formula (1), R １ represents a hydrogen atom. In formula (1Aa), Y １１ and Y １２ each independently represents an oxygen atom, a sulfur atom, or =C(CN)2. １１ and Y １２ are not identical to each other. In formula (1Aa), X 12 represents a sulfur atom, X 11 represents a nitrogen atom or —CR ｘ = represents. R ｘ represents a hydrogen atom or a substituent. ｘ =, two R ｘ They may be linked to each other to form a benzene ring which may have a substituent. In formula (1Aa), * represents a bonding position. In formula (2Aa), formula (2Ab), and formula (2Ac), Y ２１ and Y ２２ each independently represents an oxygen atom, a sulfur atom, or =C(CN)2. ２１ and Y ２２ are not identical to each other. In formula (2Aa), formula (2Ab), and formula (2Ac), X 22 represents a sulfur atom, X 21 represents a nitrogen atom or —CR ｙ = represents. R ｙ represents a hydrogen atom or a substituent. ｙ =, R ｙ They may be linked to each other to form a benzene ring which may have a substituent. In formula (2Aa), X b1 and X b2 each independently represent —CR z1 ═, where R z1 represents a hydrogen atom or a substituent. In formula (2Ab) and formula (2Ac), X b3 represents a sulfur atom. In formula (2Aa), formula (2Ab), and formula (2Ac), * represents a bonding position. In formula (5D), * represents a bonding position. In formula (5D), R d11 and R d12 each independently represent a phenyl group which may have a substituent, or —C(R L11 )(R L12 )(R L13 ). R L11 to R L13 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R L11 and R L12 may be bonded to each other to form a 3- to 6-membered cycloalkane ring. In formula (5D), R d13 represents a hydrogen atom. In formula (5D), E d51 and E d52 represent —CR E51 ═, and R E51 represents a hydrogen atom or a substituent. In formula (5D), R d54 and R d55 each independently represent a hydrogen atom or a substituent. In formula (6D), * represents a bonding position. In formula (6D), R d22 represents a phenyl group which may have a substituent, or —C(R L21 )(R L22 )(R L23 ). R L21 to R L23 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R L21 and R L22 may be bonded to each other to form a 3- to 6-membered cycloalkane ring. In formula (6D), X d21 represents a sulfur atom or —C(R L24 )(R L25 )—. R L24 to R L25 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R L24 and R L25 may be bonded to each other to form a 3- to 6-membered cycloalkane ring. In formula (6D), R d23 represents a hydrogen atom. In formula (6D), R d61 to R d64 each independently represent a hydrogen atom or a substituent, and R d61 to R d64 may be bonded to each other to form a benzene ring which may have a substituent. 【Chemistry 2】

2. The Y １１ and the Y １２ represents an oxygen atom or a sulfur atom, The Y ２１ and the Y ２２ The photoelectric conversion element according to claim 1 , wherein one of the groups represents an oxygen atom or a sulfur atom.

3. The Y １１ and the Y １２ One of them is =C(CN) ２ represents The Y ２１ and the Y ２２ One of them is =C(CN) ２ The photoelectric conversion element according to claim 1 , wherein

4. The above A １ The photoelectric conversion element according to any one of claims 1 to 3, wherein represents a group represented by formula (1Aa-1): 【Transformation 3】 (1Aa-1), R ｘ represents a hydrogen atom or a substituent. * represents a bonding position.

5. In the formula (5D), the R ｄ１１ and the above R ｄ１２ 5. The photoelectric conversion element according to claim 1, wherein the first and second electrodes have different structures.

6. In the formula (5D), the R ｄ１１ and the R ｄ１２ The photoelectric conversion element according to any one of claims 1 to 5, wherein one of the groups represents an alkyl group which may have a substituent, and the other represents a group represented by formula (X): 【Chemistry 4】 In formula (X), * represents a bonding position. １ is R ｄ１ represents a benzene ring which may have a substituent other than R. ｄ１ represents an optionally substituted alkyl group, an optionally substituted silyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, a cyano group, a halogen atom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group.

7. The photoelectric conversion element according to claim 6 , wherein the group represented by formula (X) is a group represented by formula (ZB): 【Transformation 5】 In formula (ZB), T １ ~T ３ are each independently -CR ｅ１２ = represents. R ｅ１２ represents a hydrogen atom or a substituent. ｆ３ and R ｆ４ each independently 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. * represents a bonding position.

8. The photoelectric conversion element according to any one of claims 1 to 7, wherein the formula (6D) satisfies at least one of the following requirements: Requirement X1: The above R ｄ２２ represents a phenyl group which may have a substituent. Requirement X2: Said X ｄ２１ -C(R Ｌ２４ ) (R Ｌ２５ )- and R Ｌ２４ and R Ｌ２５ and are bonded to each other to form a cycloalkane ring having 3 to 6 ring members. Requirement X3: The above R ｄ６１ and the above R ｄ６２ , the R ｄ６２ and the above R ｄ６３ , and the R ｄ６３ and the above R ｄ６４ Any one or more of the following may be bonded to each other to form a benzene ring which may have a substituent.

9. The photoelectric conversion element according to any one of claims 1 to 8, wherein the photoelectric conversion film further contains an n-type semiconductor.

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

11. The photoelectric conversion element according to any one of claims 1 to 10, wherein the photoelectric conversion film further contains a p-type semiconductor.

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

13. An imaging device comprising the photoelectric conversion element according to any one of claims 1 to 12.

14. An optical sensor comprising the photoelectric conversion element according to any one of claims 1 to 13.

15. A compound represented by the following formula (1): 【Transformation 6】 【change】 【change】 【change】 In formula (1), A １ represents a group represented by any one of formula (1Aa), formula (2Aa), formula (2Ab), and formula (2Ac). In formula (1), D １ represents a group represented by either formula (5D) or formula (6D). In formula (1), R １ represents a hydrogen atom. In formula (1Aa), Y １１ and Y １２ each independently represents an oxygen atom, a sulfur atom, or =C(CN)2. １１ and Y １２ are not identical to each other. In formula (1Aa), X 12 represents a sulfur atom, X 11 represents a nitrogen atom or —CR ｘ = represents. R ｘ represents a hydrogen atom or a substituent. ｘ =, two R ｘ They may be linked to each other to form a benzene ring which may have a substituent. In formula (1Aa), * represents a bonding position. In formula (2Aa), formula (2Ab), and formula (2Ac), Y ２１ and Y ２２ each independently represents an oxygen atom, a sulfur atom, or =C(CN)2. ２１ and Y ２２ are not identical to each other. In formula (2Aa), formula (2Ab), and formula (2Ac), X 22 represents a sulfur atom, X 21 represents a nitrogen atom or —CR ｙ = represents. R ｙ represents a hydrogen atom or a substituent. ｙ =, R ｙ They may be linked to each other to form a benzene ring which may have a substituent. In formula (2Aa), X b1 and X b2 each independently represent —CR z1 ═, where R z1 represents a hydrogen atom or a substituent. In formula (2Ab) and formula (2Ac), X b3 represents a sulfur atom. In formula (2Aa), formula (2Ab), and formula (2Ac), * represents a bonding position. In formula (5D), * represents a bonding position. In formula (5D), R d11 and R d12 each independently represent a phenyl group which may have a substituent, or —C(R L11 )(R L12 )(R L13 ). R L11 to R L13 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R L11 and R L12 may be bonded to each other to form a 3- to 6-membered cycloalkane ring. In formula (5D), R d13 represents a hydrogen atom. In formula (5D), E d51 and E d52 represent —CR E51 ═, and R E51 represents a hydrogen atom or a substituent. In formula (5D), R d54 and R d55 each independently represent a hydrogen atom or a substituent. In formula (6D), * represents a bonding position. In formula (6D), R d22 represents a phenyl group which may have a substituent, or —C(R L21 )(R L22 )(R L23 ). R L21 to R L23 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R L21 and R L22 may be bonded to each other to form a 3- to 6-membered cycloalkane ring. In formula (6D), X d21 represents a sulfur atom or —C(R L24 )(R L25 )—. R L24 to R L25 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R L24 and R L25 may be bonded to each other to form a 3- to 6-membered cycloalkane ring. In formula (6D), R d23 represents a hydrogen atom. In formula (6D), R d61 to R d64 each independently represent a hydrogen atom or a substituent, and R d61 to R d64 may be bonded to each other to form a benzene ring which may have a substituent.

16. The Y １１ and the Y １２ represents an oxygen atom or a sulfur atom, The Y ２１ and the Y ２２ 16. The compound of claim 15, wherein one of represents an oxygen atom or a sulfur atom.

17. The Y １１ and the Y １２ One of them is =C(CN) ２ represents The Y ２１ and the Y ２２ One of them is =C(CN) ２ 16. The compound of claim 15, wherein

18. The above A １ The compound according to any one of claims 15 to 17, wherein: represents a group represented by formula (1Aa-1): 【Transformation 7】 (1Aa-1), R ｘ represents a hydrogen atom or a substituent. * represents a bonding position.

19. In the formula (5D), the R ｄ１１ and the above R ｄ１２ and have different structures from each other.

20. In the formula (5D), the R ｄ１１ and the R ｄ１２ The photoelectric conversion element according to any one of claims 15 to 19, wherein one of the groups represents an alkyl group which may have a substituent, and the other represents a group represented by formula (X): 【Transformation 8】 In formula (X), * represents a bonding position. １ is R ｄ１ represents a benzene ring which may have a substituent other than R. ｄ１ represents an optionally substituted alkyl group, an optionally substituted silyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, a cyano group, a halogen atom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group.

21. The compound according to claim 20, wherein the group represented by formula (X) represents a group represented by formula (ZB): 【Chemistry 9】 In formula (ZB), T １ ~T ３ are each independently -CR ｅ１２ = represents. R ｅ１２ represents a hydrogen atom or a substituent. ｆ３ and R ｆ４ each independently 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. * represents a bonding position.

22. The compound according to any one of claims 15 to 21, wherein the formula (6D) satisfies at least one of the following requirements: Requirement X1: The above R ｄ２２ represents a phenyl group which may have a substituent. Requirement X2: Said X ｄ２１ -C(R Ｌ２４ ) (R Ｌ２５ )- and R Ｌ２４ and R Ｌ２５ and are bonded to each other to form a cycloalkane ring having 3 to 6 ring members. Requirement X3: The above R ｄ６１ and the above R ｄ６２ , the R ｄ６２ and the above R ｄ６３ , and the R ｄ６３ and the above R ｄ６４ Any one or more of the following may be bonded to each other to form a benzene ring which may have a substituent.

23. A compound represented by the following formula (1-10): 【Chemistry 10】

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