Photoelectric conversion elements, imaging elements, optical sensors, compounds

Abstract

To provide a photoelectric converter excellent in manufacturing suitability and also excellent in photoelectric conversion efficiency for a specific wavelength; and an imager, a photosensor and a compound.SOLUTION: The photoelectric converter has a conductive film, a photoelectric conversion film and a transparent conductive film in this order, where the photoelectric conversion film contains a compound represented by formula (1).SELECTED DRAWING: None

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 devices having photoelectric conversion films has progressed. For example, Patent Document 1 discloses a compound represented by the following formula as a material to be applied to photoelectric conversion devices.

[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] In recent years, with the demand for improved performance of image sensors, optical sensors, etc., further improvements in the properties required of photoelectric conversion elements used therein are being demanded. For example, photoelectric conversion elements are being demanded to have excellent manufacturability of the photoelectric conversion film thereof and excellent photoelectric conversion efficiency for green light (e.g., wavelength 500 nm, etc.) and red light (e.g., wavelength 600 nm, etc.) (hereinafter also referred to as "photoelectric conversion efficiency for specific wavelengths"). Manufacturability means that a photoelectric conversion element having excellent photoelectric conversion efficiency can be obtained even when the deposition rate of the photoelectric conversion film is increased.

[0006] The present inventors have studied photoelectric conversion elements using the compounds disclosed in Patent Document 1 and the like, and have found that it is difficult to achieve both manufacturability and photoelectric conversion efficiency at a specific wavelength.

[0007] Therefore, an object of the present invention is to provide a photoelectric conversion element that is excellent in manufacturability and photoelectric conversion efficiency at a specific wavelength. Another object of the present invention is to provide an imaging element, an optical sensor, and a compound. [Means for solving the problem]

[0008] 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.

[0009] [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 a compound represented by formula (1) described below. [2] Y a11 is an oxygen atom. [3] Ar a11 is a five-membered ring. [4] A 1 is a group represented by formula (2A) described later or a group represented by formula (3A) described later. [5] D 1 is a group represented by any one of formulas (1D) to (3D) described below. [6] D 1 is a group represented by formula (1D) described below. [7] D 1 is a group represented by formula (4D) described below. [8] D 1is a group represented by formula (5D) described below. [9] D 1 is a group represented by formula (6D) described below.

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

[11] The photoelectric conversion element according to

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

[12] The photoelectric conversion element according to

[10] or

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

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

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

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

[13] .

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

[13] .

[16] A compound represented by formula (1) described below.

[17] Y a11 is an oxygen atom.

[18] Ar a11 is a five-membered ring.

[19] A 1 is a group represented by formula (2A) described below or a group represented by formula (3A) described below.

[20] D 1 is a group represented by any one of formula (1D) to formula (3D) described later. 〔twenty one〕 D 1 is a group represented by formula (1D) described below. 〔twenty two〕 D 1 is a group represented by formula (4D) described below. 〔twenty three〕 D 1 is a group represented by formula (5D) described below. 〔twenty four〕 D 1 is a group represented by formula (6D) described below. [Effects of the Invention]

[0010] According to the present invention, a photoelectric conversion element having excellent manufacturability and excellent photoelectric conversion efficiency at a specific wavelength can be provided. Also, according to the present invention, an imaging element, an optical sensor, and a compound can be provided. [Brief explanation of the drawings]

[0011] [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

[0012] 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, unless otherwise specified, examples of the "substituent" include the groups exemplified as the substituent W described below.

[0013] (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.

[0014] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0015] In this specification, unless otherwise specified, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more 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.

[0016] 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.

[0017] In this specification, unless otherwise specified, the alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20. In the optionally substituted alkenyl group, examples of the substituent that the alkenyl group may have include the same examples as the substituent in the optionally substituted alkyl group. In this specification, unless otherwise specified, the alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20. In the alkynyl group which may have a substituent, examples of the substituent which the alkynyl group may have are the same as those of the substituent in the alkyl group which may have a substituent.

[0018] 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.

[0019] 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).

[0020] 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.

[0021] 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."

[0022] [Photoelectric conversion element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) (hereinafter also referred to as a "specific compound"). A feature of the present invention is that it contains a specific compound. The present inventors speculate that the specific compound has excellent photoelectric conversion efficiency for green and red light in the visible light region, particularly because it has a group represented by formula (1A).Furthermore, the specific compound is thought to have excellent manufacturability due to the influence of its overall structure and overall physical properties (e.g., molecular weight, etc.). Hereinafter, superior effects in at least one of photoelectric conversion efficiency for a specific wavelength and manufacturability will also be referred to as "superior effects of the present invention."

[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, 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 is incident on the photoelectric conversion film 12 through the upper electrode 15. When the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 -5 ~1×10 7 From the viewpoint of performance and power consumption, it is preferable to apply a voltage of 1×10 V / cm. -4 ~1×10 7 V / cm is more preferable, and 1×10 -3 ~5×10 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. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0025] [Photoelectric conversion film] The photoelectric conversion element has a photoelectric conversion film.

[0026] <Specific compound> The photoelectric conversion film contains a specific compound as a photoelectric conversion material. The specific compound is a compound represented by formula (1).

[0027] The specific compound has the formula (1), R 1 Formula (1) includes all geometric isomers that can be distinguished based on the C=C double bond formed by the carbon atom to which the carbon atom is bonded and the carbon atom adjacent thereto. In other words, both cis and trans isomers distinguished based on the C=C double bond are included in the compound represented by formula (1).

[0028] [ka]

[0029] In formula (1), A 1 represents a group represented by formula (1A). 1 represents a substituent having an aromatic ring. 1 represents a hydrogen atom or a substituent.

[0030] R 1 represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified as the substituent W. R 1 is preferably a hydrogen atom.

[0031] A 1 represents a group represented by formula (1A). A 1 is preferably a group represented by formula (2A) or a group represented by formula (3A).

[0032] [ka]

[0033] In formula (1A), * represents a bonding position. a11 is an oxygen atom, a sulfur atom, =NR Y11 or =CR Y12 R Y13 Represents R Y11 represents a hydrogen atom or a substituent. Y12 and R Y13 each independently represents a cyano group or -COOR Y14 Represents R Y14 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. a11 and X a12 Each of X independently represents a nitrogen atom or =C<. a11 and X a12 The solid and dotted lines between X and X represent single or double bonds. a11and X a12 If the bond with represents a double bond, X a11 and X a12 represents =C<. X a11 and X a12 If the bond with represents a single bond, X a11 and X a12 One of the groups represents a nitrogen atom, and the other represents a nitrogen atom or =C<. a11 is X a11 and X a12 represents a ring containing Ar a11 The ring represented by X may further have a substituent. a13 is a nitrogen atom or -CR X11 = R X11 represents a hydrogen atom or a substituent.

[0034] Y a11 is an oxygen atom, a sulfur atom, =NR Y11 or =CR Y12 R Y13 Represents. R Y11 represents a hydrogen atom or a substituent. Y12 and R Y13 each independently represents a cyano group or -COOR Y14 Represents R Y14 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. Y a11 is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. R Y14 Examples of the aromatic ring group represented by the formula (I) which may have a substituent include an aryl group which may have a substituent and a heteroaryl group which may have a substituent. R Y11 Substituents represented by R Y14 and the substituents which may be contained in the aromatic ring group represented by R Y14 Examples of the substituent that the alkyl group represented by the following formula may have include the groups exemplified as the substituent W.

[0035] X a11 and X a12Each of X independently represents a nitrogen atom or =C<. a11 and X a12 The solid and dotted bonds represent single or double bonds. a11 and X a12 If the bond with represents a double bond, X a11 and X a12 represents =C<. X a11 and X a12 If the bond with represents a single bond, X a11 and X a12 One of the groups represents a nitrogen atom, and the other represents a nitrogen atom or =C<. X a11 and X a12 It is preferable that at least one of the groups represents =C<. Specifically, X in formulas (1A-1) to (1A-4) described below a11 and X a12 Examples of the embodiment include the part corresponding to the above.

[0036] X a13 is a nitrogen atom or -CR X11 = R X11 represents a hydrogen atom or a substituent. X a13 As for -CR X11 = is preferred. R X11 Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W, and a halogen atom (preferably a fluorine atom), an alkyl group, or an alkyl group having a halogen atom (preferably a fluorine atom) is preferred, and an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms and a fluorine atom is more preferred. The alkyl group may be linear, branched, or cyclic, and is preferably linear.

[0037] Ar a11 is X a11 and X a12 represents a ring containing Ar a11 The ring represented by the formula (I) may further have a substituent. Ar a11 is X a11 and X a12In other words, Ar a11 The ring represented by the formula has X as a ring member atom. a11 and X a12 Includes: The above Ar a11 Examples of the substituent that the ring represented by the formula (I) may have include the groups exemplified as the substituent W, and an alkyl group that may have a substituent, a halogen atom, or a cyano group is preferred. The alkyl group may be linear, branched, or cyclic, and is preferably linear. Ar a11 The ring may be either a monocyclic ring or a polycyclic ring, and is preferably a monocyclic ring. The polycyclic ring may be a condensed ring. Ar a11 The number of carbon atoms is preferably 2 to 20, and more preferably 2 to 5. Ar a11 may have a heteroatom as a ring member atom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a nitrogen atom is preferred. Ar a11 may be either aromatic or non-aromatic, and is preferably aromatic. Ar a11 Preferably, the ring contains a 5-membered or 6-membered ring, more preferably contains a 5-membered ring, and even more preferably is a 5-membered ring (a monocyclic 5-membered ring).

[0038] Ar a11 Examples of the ring include aromatic rings such as aromatic hydrocarbon rings and aromatic heterocycles, and non-aromatic rings, with aromatic rings being preferred and aromatic heterocycles being more preferred. Ar a11Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring; aromatic heterocycles such as a pyrrole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a thiophene ring, a furan ring, a pyran ring, a thiazole ring, an oxazole ring, a selenophene ring, an imidazole ring, a benzofuran ring, a benzothiophene ring, a benzotriazole ring, and a benzoxazole ring; and non-aromatic rings such as a cycloalkane ring, a pyrrolidine ring, a pyrroline ring, an imidazolidine ring, and a tetrafuran ring.

[0039] Examples of the group represented by formula (1A) include groups represented by any of formulas (1A-1) to (1A-4).

[0040] [ka]

[0041] In the formulas (1A-1) to (1A-4), the various notations are as defined above.

[0042] [ka]

[0043] In formula (2A), * represents a bonding position. a21 represents a hydrogen atom or a substituent. a21 ~X a23 each independently represents a nitrogen atom or -CR X21 = R X21 represents a hydrogen atom or a substituent.

[0044] R a21 is the above R X11 The preferred embodiments are also the same as those described above.

[0045] X a21 ~X a23 each independently represents a nitrogen atom or -CR X21 = R X21represents a hydrogen atom or a substituent. R X21 Examples of the substituent represented by the formula: include the groups exemplified for the substituent W. R X21 is preferably a hydrogen atom. X a21 ~X a23 At least one of them is -CR X21 = is preferably represented by X a21 ~X a23 All of -CR X21 It is more preferable to represent =.

[0046] In formula (3A), * represents a bonding position. a31 and R a32 Each of X independently represents a hydrogen atom or a substituent. a31 and X a32 each independently represents a nitrogen atom or -CR X22 = R X22 represents a hydrogen atom or a substituent.

[0047] R a31 is the above R X11 The preferred embodiments are also the same as those described above. R a32 Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W, and are preferably alkyl groups, more preferably alkyl groups having 1 to 3 carbon atoms. The alkyl groups may be linear, branched, or cyclic, and are preferably linear.

[0048] X a31 and X a32 each independently represents a nitrogen atom or -CR X22 = R X22 represents a hydrogen atom or a substituent. R X22 is the above R X21 The preferred embodiments are also the same as those described above. X a31 and X a32 One represents a nitrogen atom, and the other represents -CR X22 It is preferable to represent =.

[0049] D 1 represents a substituent having an aromatic ring. The term "a substituent having an aromatic ring" means that the substituent has an aromatic ring in part or all of it. In other words, the substituent having an aromatic ring may be a group having an aromatic ring and a substituent, or an aromatic ring group having only an aromatic ring. D 1 is preferably an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and more preferably a heteroaryl group which may have a substituent. Examples of the substituent which the aryl group and the heteroaryl group may have include the groups exemplified as the substituent W, and an aryl group which may have a substituent (preferably an aryl group which may have an alkyl group) or a heteroaryl group which may have a substituent (preferably a heteroaryl group which may have an alkyl group) is preferred.

[0050] D 1 The ring may be either a monocyclic ring or a polycyclic ring. The polycyclic ring may be a condensed ring. D 1 The aromatic ring has preferably 5 to 40 ring members, more preferably 10 to 30 ring members, and further preferably 20 to 30 ring members. Examples of aromatic rings include aromatic hydrocarbon rings, aromatic heterocycles, and rings formed by combining these. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and rings formed by combining these rings. Examples of aromatic heterocycles 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, a benzothiazole ring, and rings formed by combining these. D 1 may further have another ring in addition to the aromatic ring, and the other ring may be condensed with the aromatic ring to form a condensed ring. Examples of the other ring include a cycloalkane ring, a piperidine ring, a piperazine ring, an imidazolidine ring, and a ring formed by combining these rings.

[0051] D 1 As the group represented by formula (1D), a group represented by any one of formulas (1D) to (3D) is preferred, a group represented by formula (1D) is more preferred, a group represented by formula (4D) is even more preferred, a group represented by formula (5D) is particularly preferred, and a group represented by formula (6D) is most preferred.

[0052] [ka]

[0053] In formula (1D), * represents the bonding position. d11 represents an aromatic ring containing two or more carbon atoms. d11 The aromatic ring represented by R may further have a substituent. d11 and R d12 are each independently -C(R L11 )(R L12 )(R L13 ) or an aromatic ring group which may have a substituent. L11 ~R L13 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. L11 ~R L13 The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. d13 represents a hydrogen atom or a substituent.

[0054] Ar d11 represents an aromatic ring containing two or more carbon atoms. d11 The aromatic ring represented by the formula (I) may further 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 d11Examples of the substituent that the aromatic ring represented by the formula (I) may have include the groups exemplified as the substituent W, and an optionally substituted alkyl group, a chlorine atom, a fluorine atom or a cyano group is preferred.

[0055] R d11 and R d12 are each independently -C(R L11 )(R L12 )(R L13 ) or an aromatic ring group which may have a substituent. R d11 and R d12 The aromatic ring group represented by the following formula (I) which may have a substituent is preferably an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and more preferably an aryl group which may have a substituent.

[0056] The aryl group which may have a substituent is preferably a phenyl group, a naphthyl group or a fluorenyl group which may have a substituent, and more preferably a phenyl group which may have a substituent or a naphthyl group which may have a substituent. When the aryl group which may have a substituent is a phenyl group which may have a substituent, the phenyl group preferably has a substituent, and the substituents are each independently preferably an alkyl group (preferably having 1 to 3 carbon atoms). When the aryl group which may have a substituent is a phenyl group which may have a substituent, the phenyl group preferably has 1 to 5 substituents, and more preferably has 2 or 3 substituents.

[0057] 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. R L11 ~R L13 The optionally substituted aromatic ring group represented by the following formula (I) is preferably an optionally substituted aryl group or an optionally substituted heteroaryl group. R L11 ~RL13 Preferably, at least two of these independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. R L11 ~R L13 The optionally substituted alkyl group, the optionally substituted aryl group, and the optionally substituted heteroaryl group represented by the following formula (I) may be bonded to each other to form a ring. 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. The 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 L13and 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.

[0058] R L11 ~R L13 The alkyl groups represented by R may each independently be linear, branched, or cyclic. L11 ~R L13 In the alkyl group represented by the formula: two alkyl groups are preferably bonded to each other to form a ring. More specifically, 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 alkyl groups represented by the following formula (I) may be bonded to each other to form a polycycle (for example, a polycyclic cycloalkane ring). That is, -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 5 to 8 ring members, and even more preferably 6 ring members. The cycloalkyl group may be monocyclic (eg, cyclohexyl group, etc.) or polycyclic (eg, 1-adamantyl group, etc.). The cycloalkyl group preferably has a substituent. When the cycloalkyl group has a substituent, the carbon atom directly bonded to the nitrogen atom specified in formula (1D) (i.e., "-C(R L11 )(R L12 )(R L13Preferably, the carbon atom adjacent to the "C" atom specified in ")" has a substituent. Examples of the substituent that the cycloalkyl group may have include alkyl groups (preferably having 1 to 3 carbon atoms). Substituents on 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 a ring other than a cycloalkane ring.

[0059] R d11 and R d12 are each independently a group represented by formula (X), -C(R L11 )(R L12 )(R L13 ), preferably represents an optionally substituted polycyclic aryl group or an optionally substituted polycyclic heteroaryl group. From the viewpoint of superior manufacturability of the photoelectric conversion element of the present invention, R d11 and R d12 are each independently a group represented by formula (X), -C(R L11 )(R L12 )(R L13 ) or a polycyclic aryl group which may have a substituent. The group represented by formula (X) is preferably a group represented by formula (Z) described later, and more preferably a group represented by formula (ZB) described later.

[0060] [ka]

[0061] In formula (X), C 1 is R d1 R represents a monocyclic aromatic ring which may have a substituent other than 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. These groups may further have a substituent, if possible. * represents a bonding position.

[0062] C 1is R d1 represents a monocyclic aromatic ring 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, and an oxazole ring. The monocyclic aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring, in that the heat resistance of the photoelectric conversion element is superior.

[0063] 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. These groups may further have a substituent, if possible. R d1 The alkyl group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. R d1 The silyl group represented by the following formula preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 3 carbon atoms. R d1 The alkoxy group represented by the following formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. R d1 The alkylthio group represented by the following formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. 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. R d1 The alkenyl group represented by the following formula (I) preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 or 3 carbon atoms. R d1 The alkynyl group represented by the following formula preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 or 3 carbon atoms.

[0064] R d1 and C1 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).

[0065] [ka]

[0066] In formula (Z), T 1 ~T 4 are each independently -CR e12 = or nitrogen atom (=N-). e12 represents a hydrogen atom or a substituent.

[0067] "T 1 ~T 4 At least one of the is -CR e12 = and R e12 represents a substituent group," and "at least one of T 4 Ga-CR e12 = and T 4 R in e12 represents an alkyl group, an aryl group or a heteroaryl group. R e12 The substituent represented by the formula (I) is preferably an alkyl group, an aryl group, a heteroaryl group, a silyl group, a halogen atom, or a cyano group. These groups may further have a substituent (for example, a halogen atom such as a fluorine atom). R e12 The alkyl group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. R e12 The silyl group represented by the formula: d1 Examples of the silyl group include the silyl groups described above as the silyl group represented by the following formula: R e12 Examples of the halogen atom represented by the formula (I) include a fluorine atom, an iodine atom, a bromine atom, and a chlorine atom. In addition, R in formula (Z) e12 If there are multiplee12 may be the same or different from each other.

[0068] In formula (Z), R f2 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. 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. R f2 The alkyl group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0069] [ka]

[0070] 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 is the same as:

[0071] In formula (ZB), R f3 and R f4 Each of the symbols independently represents an alkyl group, an aryl group, or a heteroaryl group. These groups may further have a substituent, if possible. * represents the bonding position. R f3 and R f4 The alkyl group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0072] The number of rings constituting the polycyclic aryl group which may have a substituent and the polycyclic heteroaryl group which may have a substituent is 2 or more, preferably 2 to 4, more preferably 2 to 3, and even more preferably 2. The substituents that the optionally substituted polycyclic aryl group and the optionally substituted polycyclic heteroaryl group may have may contain a non-aromatic ring. A preferred example of the polycyclic aryl group which may have a substituent is a naphthyl group which may have a substituent.

[0073] R d13 represents a hydrogen atom or a substituent. R d13 Examples of the substituent represented by the formula: include the groups exemplified for the substituent W. R d13 is preferably a hydrogen atom.

[0074] In formula (2D), * represents the bonding position. d21 represents an aromatic ring containing two or more carbon atoms. d21 The aromatic ring represented by Z may further have a substituent. d21 is a chalcogen atom or -NR Z21 - represents R Z21 represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. d22 is a nitrogen atom or -CR Z22 = R Z22 represents a hydrogen atom or a substituent.

[0075] Ar d21 represents an aromatic ring containing two or more carbon atoms. d21 The aromatic ring represented by the formula (I) may further have a substituent. Ar d21 Examples include Ar d11 and aromatic heterocycles are preferred. Ar d21Examples of the substituent that the aromatic ring represented by the following formula may have include the groups exemplified as the substituent W, and an alkyl group or an aryl group is preferred. Ar d21 The ring may be either a monocyclic ring or a polycyclic ring. The polycyclic ring may be a condensed ring. Ar d21 The aromatic ring represented by the formula (I) preferably has 5 to 6 ring members, more preferably 5 ring members. Examples of the aromatic heterocycle include a quinoxaline ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, and a ring formed by combining these rings, with a pyrrole ring, a furan ring, or a thiophene ring being preferred.

[0076] Z d21 is a chalcogen atom or -NR Z21 - represents R Z21 represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Examples of chalcogen atoms include oxygen atoms, sulfur atoms, selenium atoms, and tellurium atoms, with oxygen atoms and sulfur atoms being preferred. R Z21 is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably an alkyl group which may have a substituent, and even more preferably an unsubstituted alkyl group. Examples of the substituent include the groups exemplified for the substituent W, and an alkyl group is preferred. Z d21 As for -NR Z21 - is preferred.

[0077] Z d22 is a nitrogen atom or -CR Z22 = R Z22 represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified as the substituent W, and an alkyl group is preferred. R Z22 is preferably a hydrogen atom.

[0078] In formula (3D), * represents the bonding position. d31 and Ar d32 each independently represents an aromatic ring containing two or more carbon atoms. d31 and Ar d32 The aromatic ring represented by Z may further have a substituent. d31 -CR Z31 R Z32 -, -SiR Z31 R Z32 - or >C=R Z33 Represents R Z31 and R Z32 R each independently represents a hydrogen atom or a substituent. Z31 and R Z32 may be bonded to each other to form a ring. Z33 is an oxygen atom, a sulfur atom or =CR Z34 R Z35 Represents R Z34 and R Z35 R each independently represents a hydrogen atom or a substituent. Z34 and R Z35 At least one of Ar d31 and Ar d32 may be fused with at least one of R to form a fused ring. d31 represents a hydrogen atom or a substituent.

[0079] Ar d31 and Ar d32 each independently represents an aromatic ring containing two or more carbon atoms. d31 and Ar d32 The aromatic ring represented by the formula (I) may further have a substituent. The aromatic ring may be either a monocyclic ring or a polycyclic ring, and the polycyclic ring may be a condensed ring. Ar d31 and Ar d32 Preferably, one of Ar is monocyclic and the other is polycyclic; d31 is a monocyclic ring and Ar d32 is more preferably a polycyclic ring, and Ar d31 is a benzene ring and Ar d32 is more preferably a naphthalene ring. The monocyclic ring preferably has 5 to 12 ring members, and more preferably 5 to 6 ring members. The total number of ring members in the polycyclic ring is preferably 10 or more, more preferably 12 or more. The upper limit is often 20 or less. Ar d31 and Ar d32 The number of carbon atoms in the aromatic rings represented by the following formula (I) is independently 2 or more, and preferably 6 or more. The upper limit is often 20 or less, and preferably 12 or less. Ar d31 and Ar d32 Examples of the substituent that the aromatic ring represented by the following formula may have include the groups exemplified as the substituent W, and an alkyl group is preferred. Ar d31 and Ar d32 It is also preferred that the aromatic ring represented by the following formula (I) has no substituent. Ar d31 and Ar d32 Examples of aromatic rings represented by the formula include Ar a11 Examples of aromatic hydrocarbon rings and aromatic heterocycles include those represented by the following formula: The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring.

[0080] Z d31 -CR Z31 R Z32 -, -SiR Z31 R Z32 - or >C=R Z33 Represents R Z31 and R Z32 R each independently represents a hydrogen atom or a substituent. Z31 and R Z32 may be bonded to each other to form a ring. Z d31 As for -CR Z31 R Z32 - is preferred. R Z31 and R Z32 Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W, and an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms) is preferred. The alkyl group may be linear, branched, or cyclic, and is preferably linear.

[0081] R Z33 is an oxygen atom, a sulfur atom or =CR Z34 R Z35 Represents R Z34 and R Z35 each independently represents a hydrogen atom or a substituent. R Z34 and R Z35 Examples of the substituent represented by the formula: include the groups exemplified for the substituent W.

[0082] R Z34 and R Z35 At least one of Ar d31 and Ar d32 may be condensed with at least one of the following to form a condensed ring. Specifically, Ar d31 and R Z34 or R Z35 And, Ar d32 and R Z34 or R Z35 And, as well as Ar d31 , Ar d32 , R Z34 and R Z35 may be condensed with each other to form a condensed ring.

[0083] [ka]

[0084] In formula (4D), * represents a bonding position. d41 and R d42 are each independently -C(R L41 )(R L42 )(R L43 ) or an aromatic ring group which may have a substituent. L41 ~R L43 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. L41 ~R L43The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. d43 represents a hydrogen atom or a substituent. d41 ~E d44 each independently represents a nitrogen atom or -CR E41 = R E41 represents a hydrogen atom or a substituent. E41 If there are multiple R E41 They may be bonded to each other to form a ring.

[0085] R d41 and R d42 are each independently -C(R L41 )(R L42 )(R L43 ) or an aromatic ring group which may have a substituent. R d41 and R d42 As for the above R d11 and the above R d12 The preferred embodiments are also the same as those described above. R d43 represents a hydrogen atom or a substituent. R d43 As for the above R d13 The preferred embodiments are also the same as those described above.

[0086] E d41 ~E d44 each independently represents a nitrogen atom or -CR E41 = R E41 represents a hydrogen atom or a substituent. E41 If there are multiple R E41 They may be bonded to each other to form a ring. E d41 ~E d44 At least two of the groups are preferably nitrogen atoms, and at least E d41 and E d44 is more preferably a nitrogen atom, and E d41 and E d44 It is more preferred that only nitrogen atoms are present. Multiple Rs E41 The ring formed by bonding together is preferably an aromatic ring, more preferably a benzene ring or a pyridine ring. The ring formed above may further have a substituent (for example, a group exemplified as the substituent W).

[0087] [ka]

[0088] In formula (5D), * represents a bonding position. d51 and R d52 are each independently -C(R L51 )(R L52 )(R L53 ) or an aromatic ring group which may have a substituent. L51 ~R L53 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. L51 ~R L53 The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. d53 ~R d55 R each independently represents a hydrogen atom or a substituent. d54 and R d55 may be bonded to each other to form a ring.

[0089] R d51 and R d52 As for the above R d11 and the above R d12 The preferred embodiments are also the same as those described above. R d53 ~R d55 each independently represents a hydrogen atom or a substituent. R d53 As for the above R d13 The preferred embodiments are also the same as those described above. R d54 and R d55 Examples of the substituent represented by the formula: include the groups exemplified for the substituent W, and an alkyl group is preferred. R d54 and R d55 The ring formed by bonding together is preferably an aromatic ring, more preferably a benzene ring. The ring formed above may further have a substituent (for example, a group exemplified as the substituent W).

[0090] [ka]

[0091] In formula (6D), * represents a bonding position. d61 and R d62 are each independently -C(R L61 )(R L62 )(R L63 ) or an aromatic ring group which may have a substituent. L61 ~R L63 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. L61 ~R L63 The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. d63 ~R d65 R each independently represents a hydrogen atom or a substituent. d64 and R d65 may be bonded to each other to form a ring. d61 and E d62 each independently represents a nitrogen atom or -CR E61 = R E61 represents a hydrogen atom or a substituent.

[0092] R d61 and R d62 As for the above R d41 and the above R d42 The preferred embodiments are also the same as those described above. R d63 ~R d65 each independently represents a hydrogen atom or a substituent. R d63 As for the above R d13The preferred embodiments are also the same as those described above. R d64 and R d65 Examples of the substituent represented by the formula: include the groups exemplified for the substituent W. R d64 and R d65 is preferably a hydrogen atom, a halogen atom or a cyano group.

[0093] E d61 and E d62 each independently represents a nitrogen atom or -CR E61 = R E61 represents a hydrogen atom or a substituent. E d61 and E d62 One of them is -CR E61 =, and the other is a nitrogen atom or -CR E61 =, and E d61 and E d62 Ga-CR E61 It is preferable to represent =. R E61 Examples of the substituent represented by the formula: include the groups exemplified for the substituent W.

[0094] Suitable embodiments of the specific compound include, for example, the following. As a preferred embodiment of the specific compound, embodiment A is preferred, embodiment B is more preferred, embodiment C is further preferred, and embodiment D is particularly preferred. Aspect A:D 1 is a substituent containing an aromatic ring, and A 1 is a group represented by formula (2A). Mode B:D 1 is a group represented by any one of formulas (1D) to (3D), and A 1 is a group represented by formula (2A) or a group represented by formula (3A). Aspect C:D 1 is a group represented by formula (5D), and A 1 is a group represented by formula (2A) or a group represented by formula (3A). Aspect D:D 1 is a group represented by formula (6D), and A 1is a group represented by formula (2A) or a group represented by formula (3A).

[0095] Examples of specific compounds are shown below. When the specific compounds exemplified below are applied to formula (1), R 1 The specific compounds exemplified below include all geometric isomers that can be distinguished based on the C=C double bond formed by the carbon atom to which the carbon atom is bonded and the carbon atom adjacent thereto. In other words, both the cis isomer and the trans isomer distinguished based on the C=C double bond are included in the specific compounds exemplified below.

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] The molecular weight of the specific compound is not particularly limited, but is preferably from 400 to 1200, more preferably from 400 to 1000, and even more preferably from 400 to 800, from the viewpoint of excellent manufacturability. When the molecular weight is within the above range, it is presumed that the sublimation temperature of the specific compound is low, and the photoelectric conversion efficiency is excellent even when the photoelectric conversion film is formed at high speed.

[0100] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, a photosensor, or a photovoltaic cell. The specific compound often functions as a p-type organic semiconductor in the photoelectric conversion film. The specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic agent material.

[0101] The specific compound is preferably a compound having an ionization potential of −5.0 to −6.0 eV in a single film, from the viewpoints of stability when used as a p-type organic semiconductor and matching of the energy level with an n-type organic semiconductor.

[0102] The maximum absorption wavelength of the specific compound is preferably in the range of 500 to 600 nm, more preferably in the range of 530 to 580 nm. The maximum absorption wavelength is a value measured in the state of a film of the specific compound (for example, a vapor-deposited film of the specific compound).

[0103] The particular compound may be purified if necessary. The method for purifying the specific compound is not particularly limited, but sublimation purification is preferred. The purity of the specific compound after sublimation purification (for example, purity measured by HPLC or GC) is not particularly limited, but is preferably 95% or more, more preferably 98% or more, and even more preferably 99% or more.

[0104] Before the specific compound is purified by sublimation, the specific compound may be purified by other methods. For example, the specific compound is preferably subjected to purification using silica gel column chromatography, purification using GPC (Gel Permeation Chromatography), reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification. The purity of the specific compound before sublimation purification (for example, purity measured by HPLC or GC) is not particularly limited, but is preferably 95% or more, more preferably 98% or more, and even more preferably 99% or more. The solvent used for recrystallization purification (recrystallization solvent) is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, butanol, toluene, xylene, anisole, 1,2-dimethoxybenzene, tetralin, chlorobenzene, dichlorobenzene, hexane, heptane, octane, acetonitrile, benzonitrile, acetic acid, chloroform, dichloromethane, ethyl acetate, butyl acetate, tetrahydrofuran, 4-methyltetrahydropyran, and cyclopentyl methyl ether. The recrystallization solvent may be a mixed solution of a plurality of solvents.

[0105] The amount of residual solvent contained in the crude product containing the specific compound to be subjected to sublimation purification is not particularly limited, but with respect to the total molar amount of the specific compound in the crude product, the amount of residual solvent is preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 2 mol% or less.

[0106] Impurities contained in the crude product containing the specific compound to be subjected to sublimation purification, which are elements that do not constitute the specific compound (for example, Li, Na, K, Mg, Ca, Al, Si, P, Sn, transition metal elements, etc.), are not particularly limited, but with respect to the total mass of the crude product, it is preferably 1000 mass ppm or less, more preferably 100 mass ppm or less, and still more preferably 10 mass ppm or less. Examples of the measurement method for the above elements include ICP (high-frequency inductively coupled plasma) emission spectrometry. M

[0107] The specific compound can be synthesized by known methods. In order to improve the purity of the specific compound, the purity of the raw materials used in the synthesis of the specific compound containing the intermediate (for example, the measured purity by HPLC or GC) is not particularly limited, but 97% or more is preferable, 98% or more is more preferable, and 99% or more is still more preferable. When the purity of commercially available raw materials and synthetic intermediates is low, those purified by known methods may be used.

[0108] The specific compound may be used alone or in combination of two or more. 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 75% by volume, more preferably 20 to 60% by volume, and still more preferably 25 to 50% by volume.

[0109] <n-type organic semiconductor> The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the above specific compound. The n-type organic semiconductor is a compound different from the above specific compound. An n-type organic semiconductor is an acceptor organic semiconductor material (compound) that has the property of readily accepting electrons. In other words, an n-type organic semiconductor is the organic compound that has the greater electron affinity when two organic compounds are used in contact. In other words, any organic compound that has electron-accepting properties can be used as an acceptor organic semiconductor. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof, fused aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyridine ... pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, azoles, imidazoles, thiazoles, etc.); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives and 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] to

[0057] of JP 2006-100767 A.

[0110] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerene and derivatives thereof are preferred. 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 are compounds described in JP-A-2007-123707.

[0111] As the n-type organic semiconductor, an organic dye may be used. Examples of organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0112] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0113] It is also preferable that the n-type organic semiconductor is colorless or has a maximum absorption wavelength and / or absorption waveform similar to those of a specific compound. Specifically, the maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or in the range of 500 to 600 nm.

[0114] The photoelectric conversion film preferably has a bulk heterostructure formed by mixing a specific compound with an n-type organic semiconductor. The bulk heterostructure is a layer in the photoelectric conversion film in which the specific compound and the n-type organic semiconductor are mixed and dispersed. The photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs

[0013] to

[0014] of JP 2005-303266 A.

[0115] When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (=film thickness of n-type organic semiconductor in terms of a single layer / film thickness of 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 n-type semiconductor material may be used alone or in combination of two or more.

[0116] Furthermore, when the n-type semiconductor material contains fullerenes, the content of the fullerenes relative to the total content of the n-type semiconductor material (=film thickness of fullerenes converted into a single layer / total film thickness of each n-type semiconductor material converted into a single layer × 100) is preferably 50 to 100% by volume, and more preferably 80 to 100% by volume. The fullerenes may be used singly or in combination of two or more.

[0117] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0118] From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (=film thickness of the specific compound in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the n-type organic semiconductor in terms of a single layer)×100) is preferably 20 to 80% by volume, and more preferably 40 to 80% by volume. Also, when the photoelectric conversion film contains a p-type organic semiconductor described below, the content of the specific compound (= film thickness in terms of a single layer of the specific compound / (film thickness in terms of a single layer of the specific compound + film thickness in terms of a single layer of the n-type organic semiconductor + film thickness in terms of a single layer of the p-type organic semiconductor) × 100) is preferably 15 to 75% by volume, more preferably 30 to 75% by volume. In addition, the photoelectric conversion film is preferably substantially composed of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor contained as desired. "Substantially" means that the total content of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor contained as desired is 90 to 100% by volume (preferably 95 to 100% by volume, more preferably 99 to 100% by volume) with respect to the total mass of the photoelectric conversion film.

[0119] <p-type organic semiconductor> The photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the above specific compound. The p-type organic semiconductor is a compound different from the above specific compound. The p-type organic semiconductor is a donor-type organic semiconductor material (compound), which refers to an organic compound having a property of easily donating electrons. That is, the p-type organic semiconductor refers to the organic compound with a smaller ionization potential when two organic compounds are brought into contact and used. The p-type organic semiconductor may be used alone or in combination of two or more.

[0120] Examples of p-type organic semiconductors 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

[0052] to

[0063] of JP-A No. 2011-225544, compounds described in paragraphs

[0119] to

[0158] of JP-A No. 2015-1 compounds described in paragraphs

[0044] to

[0051] of JP-A No. 53910 and the compounds described in paragraphs

[0086] to

[0090] of JP-A No. 2012-94660), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b]thiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, JP-A No. 2012-94660, etc.), compounds described in paragraphs

[0031] to

[0036] of WO 2018-014474; compounds described in paragraphs

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

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

[0015] to

[0025] of WO 2018-207722; compounds described in paragraphs

[0045] to

[0053] of JP 2019-054228; the compounds described in paragraphs

[0045] to

[0055] of JP-A-2019-081416, the compounds described in paragraphs

[0063] to

[0089] of WO2019-081416, the compounds described in paragraphs

[0033] to

[0036] of JP-A-2019-80052, the compounds described in paragraphs

[0044] to

[0054] of WO2019-054125, the compounds described in paragraphs

[0041] to

[0046] of WO2019-093188, the compounds described in paragraphs

[0034] to

[0037] of JP-A-2019-050398, the compounds described in paragraphs

[0033] to

[0036] of JP-A-2018-206878,The compound of paragraph

[0038] of JP 2018-190755 A, the compound of paragraphs

[0019] to

[0021] of JP 2018-026559 A, the compound of paragraphs

[0031] to

[0056] of JP 2018-170487 A, the compound of paragraphs

[0036] to

[0041] of JP 2018-078270 A, the compound of paragraphs

[0055] to

[0082] of JP 2018-11 The compounds of paragraphs

[0041] to

[0050] of JP 3425 A, the compounds of paragraphs

[0044] to

[0048] of JP 2018-85430 A, the compounds of paragraphs

[0041] to

[0045] of JP 2018-056546 A, the compounds of paragraphs

[0042] to

[0049] of JP 2018-046267 A, the compounds of paragraphs

[0031] to

[0036] of JP 2018-014474 A, WO2018-01646 Examples of the compounds include compounds described in paragraphs

[0036] to

[0046] of Japanese Patent Application Laid-Open No. 2020-010024, paragraphs

[0045] to

[0048] , cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, fused aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. Examples of p-type organic semiconductors include compounds with a smaller ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type semiconductor compounds are given below.

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0126] When the photoelectric conversion film contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the photoelectric conversion film (=film thickness of p-type organic semiconductor in single layer equivalent / film thickness of 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 material may be used alone or in combination of two or more.

[0127] A photoelectric conversion film containing a specific compound is a non-luminescent film and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode). A non-luminescent film is intended to mean a film with a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less. The lower limit is often 0% or more.

[0128] <Film formation method> The photoelectric conversion film may be formed by, for example, a dry film formation method. Examples of dry film formation methods include vapor deposition (particularly 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 a 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.

[0129] 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 300 nm.

[0130] [electrode] The photoelectric conversion element preferably has an electrode. 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, FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole. From the viewpoints of high conductivity and transparency, conductive metal oxides are preferred.

[0131] Generally, when a conductive film is made thinner than a certain range, the resistance value often increases sharply. In a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10,000 Ω / □, and there is a large degree of freedom in the range of the film thickness that can be reduced. Furthermore, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher the light transmittance. An increase in light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and enhances the photoelectric conversion capacity. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance that accompany a thinner film, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0132] 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, 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; 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; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.

[0133] The method for forming the electrode 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, methods include an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), and coating of a dispersion of indium tin oxide.

[0134] [Charge blocking film: electron blocking film, hole blocking film] The photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. The intermediate layer may be, for example, a charge-blocking film. If the photoelectric conversion element has this film, the resulting photoelectric conversion element will have better properties (such as photoelectric conversion efficiency and responsiveness). Examples of the charge-blocking film include an electron-blocking film and a hole-blocking film.

[0135] <Electron blocking film> The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. 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, as well as derivatives thereof.

[0136] The electron blocking film may be made up 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.

[0137] <Hole-blocking film> The hole-blocking film is an acceptor organic semiconductor material (compound), and the above-mentioned n-type y organic semiconductor can be used. The hole blocking film may be made up of multiple films.

[0138] Examples of methods for producing a charge-blocking film include dry film formation and wet film formation. Examples of dry film formation include vapor deposition and sputtering. Vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition such as vacuum deposition being preferred. Wet film formation includes inkjet printing, spray printing, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with inkjet printing being preferred from the standpoint of high-precision patterning.

[0139] The thickness of each of the charge blocking films (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm.

[0140] <Substrate> The photoelectric conversion element may further include a substrate. Examples of the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate. The position of the substrate is not particularly limited, but typically, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated in this order on the substrate.

[0141] <Sealing layer> The photoelectric conversion element may further include a sealing layer. The performance of photoelectric conversion materials can be significantly degraded in 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 made of ceramics such as dense metal oxide, metal nitride, or metal nitride oxide, or diamond-like carbon (DLC), which does not allow water molecules to penetrate. The sealing layer is described, for example, in paragraphs

[0210] to

[0215] of JP-A No. 2011-082508, the contents of which are incorporated herein by reference.

[0142] [Image sensor] Photoelectric conversion elements are used, for example, as imaging elements. An imaging device 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 device. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0143] [Optical sensor] Other uses of the photoelectric conversion element include, for example, photocells and optical sensors, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged linearly, or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.

[0144] [Compound] The present invention also includes inventions of compounds. The compounds of the present invention are the above-mentioned specific compounds. [Example]

[0145] 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.

[0146] [Compounds used in photoelectric conversion films] [Synthesis of Compound (D-1)] Compound (D-1) was synthesized according to the following scheme.

[0147] [ka]

[0148] 1-Aminopyrrole (3.0 g, 35.8 mmol), ethyl 4,4,4-trifluoroacetoacetate (7.25 g, 39.4 mmol), p-toluenesulfonic acid hydrate (1.34 g, 7.16 mmol), and toluene (120 mL) were stirred at 100 °C for 1 hour. The resulting reaction solution was allowed to cool to room temperature, insoluble matter was removed by filtration through Celite, and the filtrate was concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent (volume ratio): dichloromethane / ethyl acetate = 80:20) to obtain compound (D-1-1) (1.50 g, 21% yield).

[0149] To a mixture of 2,6-xylidine (300 g, 2.48 mol) and isopropanol (300 mL), 30% hydrochloric acid (288 mL, 2.73 mol) was added dropwise, and the resulting reaction mixture was stirred under reflux for 1 hour. The mixture was cooled to 2°C, and the resulting crystals were filtered. The resulting crystals were washed with isopropanol and then hexane to obtain 2,6-xylidine hydrochloride (350 g, 90% yield). Subsequently, 50% aqueous sodium hydroxide solution (199 g, 2.48 mol) was added dropwise to a mixture of 2,6-xylidine hydrochloride (300 g, 1.90 mol) and water (600 mL), and the resulting reaction mixture was stirred at room temperature (25°C) for 1 hour. The resulting mixture was transferred to a separatory funnel, washed with hexane (150 mL), and the aqueous phase was removed. The resulting organic phase was concentrated under reduced pressure to obtain 2,6-xylidine (200 g, 87%).

[0150] To a mixture of 2,3-dichloroquinoxaline (8.0 g, 40.2 mmol), a 35% tetrahydrofuran solution of sodium hexamethyldisilazane (1.9 mol / L) (90.4 mL, 181 mol), and tetrahydrofuran (80 mL), the 2,6-xylidine (11 mL, 88.2 mmol) obtained above was added dropwise. After stirring at 60°C for 1 hour, the mixture was allowed to cool to room temperature, and water (40 mL) was added dropwise. 20% by mass brine (80 mL) was added, and the organic phase was extracted. The organic phase obtained was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product obtained was recrystallized using a toluene / 2-propanol mixture to obtain intermediate (D-1-2) (9.95 g, yield 67%).

[0151] p-Toluenesulfonic acid hydrate (9.3 g, 48.9 mmol), acetic anhydride (16 mL), and intermediate (D-1-2) (6.0 g, 16.3 mmol) were added and stirred at 130 °C for 1 hour. The resulting reaction solution was allowed to cool to room temperature and added dropwise to a mixture of 50% by mass / volume aqueous sodium hydroxide (48 mL) and ice (143 g), followed by stirring for 30 minutes. Acetic acid was added to the reaction mixture to adjust the pH to 8, and the mixture was stirred for an additional 20 minutes. The resulting precipitate was filtered and washed with water and then methanol. The resulting crude product was reprecipitated from a dichloromethane / methanol mixture to obtain intermediate (D-1-3) (6.2 g, 98% yield).

[0152] To a mixture of (chloromethylene)dimethyliminium chloride (5.87 g, 45.9 mmol) and acetonitrile (60 mL), intermediate (D-1-3) (6.0 g, 15.3 mmol) was added and stirred at 50 °C for 2 hours. The reaction solution was allowed to cool to room temperature and then added dropwise to a mixture of 1 mol / L aqueous sodium hydroxide solution (90 mL) and ice (90 g), followed by stirring for 1 hour. The resulting precipitate was filtered and washed with water and then methanol. The resulting crude product was reprecipitated from a mixture of dichloromethane and acetonitrile to obtain intermediate (D-1-4) (4.4 g, yield 68%).

[0153] Intermediate (D-1-4) (0.80 g, 1.64 mmol), intermediate (D-1-1) (0.43 g, 2.13 mmol), and acetic anhydride (375 mL) were mixed and stirred at 130 °C for 30 hours. After the reaction solution was allowed to cool to room temperature, the resulting precipitate was filtered and washed with methanol. The resulting crude product was purified by silica gel chromatography (eluent (volume ratio): dichloromethane / ethyl acetate = 96:4) to obtain compound (D-1) (0.41 g, 37% yield).

[0154] The compounds used in the photoelectric conversion film other than the compound (D-1) were synthesized with reference to the synthesis method of the compound (D-1) described above. Each compound is shown below. The compounds (D-1) to (D-13) are specific compounds, and the compounds (R-1) to (R-2) are comparative compounds.

[0155] [ka]

[0156] [ka]

[0157] [n-type organic semiconductor] C60: Fullerene (C 60 )

[0158] [p-type organic semiconductor]

[0159] [ka]

[0160] 〔evaluation〕 [Fabrication of photoelectric conversion element] The obtained compound was used to fabricate a photoelectric conversion element having the configuration shown in Fig. 1. The photoelectric conversion element here comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, and an upper electrode 15. Specifically, amorphous ITO was deposited on a glass substrate by sputtering to form a lower electrode 11 (film thickness: 30 nm), and the following compound (EB-1) was further deposited on the lower electrode 11 by vacuum thermal evaporation to form an electron blocking film 16A (film thickness: 30 nm). Furthermore, with the temperature of the substrate controlled at 25°C, each specific compound and an n-type organic semiconductor (fullerene (C 60 )) were co-deposited by vacuum evaporation to form a film of 80 nm in monolayer equivalent. This resulted in the formation of a photoelectric conversion film 12 having a bulk heterostructure of 160 nm (240 nm when a p-type semiconductor material was also used). The film formation rate of the photoelectric conversion film 12 was 1.0 Å / sec. Furthermore, an upper electrode 15 (transparent conductive film) (film thickness: 10 nm) was formed by sputtering amorphous ITO on the photoelectric conversion film 12. After forming an SiO film as a sealing layer on the upper electrode 15 by vacuum deposition, an aluminum oxide (Al2O3) layer was formed thereon by ALCVD (Atomic Layer Chemical Vapor Deposition), thereby producing a photoelectric conversion element (element (A)).

[0161] [ka]

[0162] [Evaluation of photoelectric conversion efficiency (external quantum efficiency)] The operation of each of the obtained photoelectric conversion elements (element (A)) was confirmed. 5 A voltage was applied to achieve an electric field strength of 1000 V / cm. Light was then irradiated from the upper electrode (transparent conductive film) side, and IPCE (incident photon-to-current conversion efficiency) measurements were performed to extract the photoelectric conversion efficiencies (external quantum efficiencies) at wavelengths of 500 nm and 600 nm. The photoelectric conversion efficiency was measured using an Optel constant energy quantum efficiency measurement device. The irradiated light intensity was 50 μW / cm. 2 When the photoelectric conversion efficiency of the photoelectric conversion element of Example 1 was normalized to 1, the photoelectric conversion efficiency of each photoelectric conversion element was determined, and the elements were evaluated according to the following criteria based on the determined photoelectric conversion efficiency. A: 0.9 or higher B: 0.8 or more, less than 0.9 C: 0.7 or more, less than 0.8 D: Less than 0.7 For both the wavelength of 500 nm and the wavelength of 600 nm, it is preferable that the optical transparency is C or higher, and it is most preferable that the optical transparency is A. Furthermore, it was confirmed that the photoelectric conversion elements (element (A)) of each example or comparative example all exhibited a photoelectric conversion efficiency of 40% or more at wavelengths of 500 nm and 600 nm, and had an external quantum efficiency of a certain level or higher as photoelectric conversion elements.

[0163] [Evaluation of manufacturability (photoelectric conversion efficiency during high-speed film formation)] Photoelectric conversion elements (elements (B)) of each example or comparative example were produced in the same manner as element (A), except that the deposition rate of the photoelectric conversion film 12 was set to 3.0 Å / sec. Using the obtained elements (B), the photoelectric conversion efficiency (external quantum efficiency) was evaluated in the same manner as described in the section [Evaluation of photoelectric conversion efficiency (external quantum efficiency)]. The photoelectric conversion efficiencies of element (A) and element (B) of the same Example or Comparative Example were compared, and the value of "photoelectric conversion efficiency of element (B) / photoelectric conversion efficiency of element (A)" was calculated. The obtained value was used to evaluate the manufacturing suitability of each photoelectric conversion element in light of the following criteria. A: 0.90 or higher B: Less than 0.90

[0164] [Responsiveness evaluation] The response of each element (A) was evaluated. 5 A voltage was applied to achieve an intensity of 1000 V / cm. Then, an LED (light-emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 580 nm was measured with an oscilloscope. The rise time from 0% signal intensity to 97% signal intensity was measured. Next, the rise time of the photoelectric conversion element using compound (D-1) at a wavelength of 580 nm was normalized to 1, and the relative value of the rise time of each element (A) relative to the rise time of element (A) using compound (D-1) was calculated (relative value of the rise time of each element (A) / rise time of element (A) using compound (D-1)). The obtained values ​​were evaluated according to the following criteria. In practical use, D or higher is preferable, and A is most preferable. A: Less than 1.0 B: 1.0 or more and less than 2.0 C: 2.0 or more and less than 3.0 D:3.0 or more

[0165] Table 1 shows the evaluation results. The notations in Table 1 indicate the following: "D 1" column is D 1 Specifically, in the case of specific compound (D-1), D 1 corresponds to all of formulas (1D) and (4D) to (6D), but only formula (6D), which is the most subordinate concept among the above, will be described. In addition, the above D 1 The order of concepts in the formula is formula (1D) to formula (3D) / formula (4D) / formula (5D) / formula (6D). "A 1 " column, A 1 Specifically, in the case of specific compound (D-1), A 1 corresponds to both formula (1A) and formula (2A), but only formula (2A), which is the most subordinate concept, will be described below. In addition, the above A 1 The order of concepts in the formula (1A) / formula (2A) and formula (3A) are subordinate concepts in this order. "Y a11 " column, "A 1 " corresponds to formula (1A), and Y in formula (1A) a11 , or Y in a specific compound a11 If the part corresponding to is an oxygen atom, it is written as "O", and if it is a sulfur atom, it is written as "S". "Ar a11 The "Number of ring members" column is "A 1 " corresponds to formula (1A), and Ar in formula (1A) a11 , or Ar in a specific compound a11 If the number of ring members in the part corresponding to is 5, it is recorded as "5", and if it is 6, it is recorded as "6".

[0166] [Table 1]

[0167] From the results shown in the above table, it was confirmed that the photoelectric conversion element of the present invention can obtain the desired effects. Y a11It has been confirmed that when is an oxygen atom, the effects of the present invention are more excellent (comparison between Examples 1-6 and 1-7, etc.). Ar a11 It was confirmed that when is a five-membered ring, the effects of the present invention are more excellent (comparison of Examples 1-5 to 1-9, etc.). A 1 It was confirmed that when is a group represented by formula (2A) or a group represented by formula (3A), the responsiveness is more excellent (comparison between Examples 1-1 to 1-2 and 1-6, etc.). D 1 It has been confirmed that when is a group represented by any one of formulas (1D) to (3D), the effects of the present invention are more excellent (comparison of Examples 1-1 and 1-10 to 1-13, etc.). 1 It has been confirmed that the effects of the present invention are more excellent when is a group represented by formula (1D) (preferably formula (5D), more preferably formula (6D)). It was confirmed that when the photoelectric conversion film further contained an n-type organic semiconductor and a p-type organic semiconductor, the response was more excellent (comparison between Examples 1-1, 1-14 and 1-15, etc.). [Explanation of symbols]

[0168] 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 a compound represented by formula (1): However, the compound represented by the formula (1) does not have a carboxy group or a salt thereof. 【Chemical 1】 In formula (1), A １ represents a group represented by formula (1A). １ represents a substituent having an aromatic ring. １ represents a hydrogen atom or a substituent. 【Chemistry 2】 In formula (1A), * represents a bonding position. ａ１１ represents an oxygen atom, a sulfur atom, and ═NR Ｙ１１ or =CR Ｙ１２ R Ｙ１３ Represents R Ｙ１１ represents a hydrogen atom or a substituent. Ｙ１２ and R Ｙ１３ each independently represents a cyano group or —COOR Ｙ１４ Represents R Ｙ１４ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. X ａ１１ and X ａ１２ each independently represents a nitrogen atom or =C<. ａ１１ and X ａ１２ The bonds represented by solid and dotted lines represent single or double bonds. ａ１１ and X ａ１２ When the bond with represents a double bond, X ａ１１ and X ａ１２ represents =C<. X ａ１１ and X ａ１２ When the bond with represents a single bond, X ａ１１ and X ａ１２ One of X represents a nitrogen atom, and the other represents a nitrogen atom or ═C<. ａ１３ is a nitrogen atom or -CR Ｘ１１ = represents. R Ｘ１１ represents a hydrogen atom or a substituent. ａ１１ is X ａ１１ and X ａ１２ represents a ring containing ａ１１ The ring represented by the formula (I) may further have a substituent.

2. Y ａ１１ The photoelectric conversion element according to claim 1 , wherein is an oxygen atom.

3. Ar ａ１１ The photoelectric conversion element according to claim 1 or 2, wherein is a five-membered ring.

4. A １ The photoelectric conversion element according to any one of claims 1 to 3, wherein is a group represented by formula (2A) or a group represented by formula (3A). 【Chemistry 3】 In formula (2A), * represents a bonding position. ａ２１ represents a hydrogen atom or a substituent. ａ２１ ~X ａ２３ are each independently a nitrogen atom or —CR Ｘ２１ = represents. R Ｘ２１ represents a hydrogen atom or a substituent. In formula (3A), * represents a bonding position. ａ３１ and R ａ３２ each independently represents a hydrogen atom or a substituent. ａ３１ and X ａ３２ are each independently a nitrogen atom or —CR Ｘ２２ = represents. R Ｘ２２ represents a hydrogen atom or a substituent.

5. D １ The photoelectric conversion element according to any one of claims 1 to 4, wherein is a group represented by any one of formulas (1D) to (3D): 【Chemistry 4】 In formula (1D), * represents a bonding position. ｄ１１ represents an aromatic ring containing two or more carbon atoms. ｄ１１ The aromatic ring represented by R may further have a substituent. ｄ１１ and R ｄ１２ are each independently -C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ) or an aromatic ring group which may have a substituent. Ｌ１１ ~R Ｌ１３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ１１ ~R Ｌ１３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ１３ represents a hydrogen atom or a substituent. In formula (2D), * represents a bonding position. ｄ２１ represents an aromatic ring containing two or more carbon atoms. ｄ２１ The aromatic ring represented by the formula (I) may further have a substituent. ｄ２１ represents a chalcogen atom or -NR Ｚ２１ - represents. Ｚ２１ represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. ｄ２２ is a nitrogen atom or -CR Ｚ２２ = represents. R Ｚ２２ represents a hydrogen atom or a substituent. In formula (3D), * represents a bonding position. ｄ３１ and Ar ｄ３２ each independently represents an aromatic ring containing two or more carbon atoms. ｄ３１ and Ar ｄ３２ The aromatic ring represented by the formula (I) may further have a substituent. ｄ３１ is -CR Ｚ３１ R Ｚ３２ -, -SiR Ｚ３１ R Ｚ３２ - or > C=R Ｚ３３ Represents R Ｚ３１ and R Ｚ３２ R each independently represents a hydrogen atom or a substituent. Ｚ３１ and R Ｚ３２ may be bonded to each other to form a ring. Ｚ３３ represents an oxygen atom, a sulfur atom, or ═CR Ｚ３４ R Ｚ３５ Represents R Ｚ３４ and R Ｚ３５ R each independently represents a hydrogen atom or a substituent. Ｚ３４ and R Ｚ３５ and Ar ｄ３１ and Ar ｄ３２ may be condensed with at least one of R to form a condensed ring. ｄ３１ represents a hydrogen atom or a substituent.

6. D １ The photoelectric conversion element according to claim 5 , wherein is a group represented by formula (1D).

7. D １ The photoelectric conversion element according to any one of claims 1 to 6, wherein is a group represented by formula (4D): 【Chemistry 5】 In formula (4D), * represents a bonding position. ｄ４１ and R ｄ４２ are each independently -C(R Ｌ４１ ) (R Ｌ４２ ) (R Ｌ４３ ) or an aromatic ring group which may have a substituent. Ｌ４１ ~R Ｌ４３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ４１ ~R Ｌ４３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ４３ represents a hydrogen atom or a substituent. ｄ４１ ~E ｄ４４ are each independently a nitrogen atom or —CR Ｅ４１ = represents. R Ｅ４１ represents a hydrogen atom or a substituent. Ｅ４１ If there are multiple R Ｅ４１ They may be bonded to each other to form a ring.

8. D １ The photoelectric conversion element according to any one of claims 1 to 7, wherein is a group represented by formula (5D): 【Chemistry 6】 In formula (5D), * represents a bonding position. ｄ５１ and R ｄ５２ are each independently -C(R Ｌ５１ ) (R Ｌ５２ ) (R Ｌ５３ ) or an aromatic ring group which may have a substituent. Ｌ５１ ~R Ｌ５３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ５１ ~R Ｌ５３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ５３ ~R ｄ５５ R each independently represents a hydrogen atom or a substituent. ｄ５４ and R ｄ５５ may be bonded to each other to form a ring.

9. D １ The photoelectric conversion element according to any one of claims 1 to 8, wherein is a group represented by formula (6D): 【Chemistry 7】 In formula (6D), * represents a bonding position. ｄ６１ and R ｄ６２ are each independently -C(R Ｌ６１ ) (R Ｌ６２ ) (R Ｌ６３ ) or an aromatic ring group which may have a substituent. Ｌ６１ ~R Ｌ６３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ６１ ~R Ｌ６３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ６３ ~R ｄ６５ R each independently represents a hydrogen atom or a substituent. ｄ６４ and R ｄ６５ may be bonded to each other to form a ring. ｄ６１ and E ｄ６２ are each independently a nitrogen atom or —CR Ｅ６１ = represents. R Ｅ６１ represents a hydrogen atom or a substituent.

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

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

12. The photoelectric conversion element according to claim 10 , wherein the photoelectric conversion film further contains a p-type organic semiconductor.

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

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

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

16. A compound represented by formula (1): However, the compound represented by the formula (1) does not have a carboxy group or a salt thereof. 【Chemistry 8】 In formula (1), A １ represents a group represented by formula (1A) or formula (1A-3). １ represents a substituent having an aromatic ring. １ represents a hydrogen atom or a substituent. 【Chemistry 9】 In formula (1A), * represents a bonding position. ａ１１ represents an oxygen atom, a sulfur atom, and ═NR Ｙ１１ or =CR Ｙ１２ R Ｙ１３ Represents R Ｙ１１ represents a hydrogen atom or a substituent. Ｙ１２ and R Ｙ１３ each independently represents a cyano group or —COOR Ｙ１４ Represents R Ｙ１４ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. X ａ１１ represents a nitrogen atom or =C<. ａ１２ represents =C<. X ａ１１ and X ａ１２ The bonds represented by solid and dotted lines represent single or double bonds. ａ１１ and X ａ１２ When the bond with represents a double bond, X ａ１１ and X ａ１２ represents =C<. X ａ１１ and X ａ１２ When the bond with represents a single bond, X ａ１１ and X ａ１２ One of X represents a nitrogen atom, and the other represents a nitrogen atom or ═C<. ａ１３ is a nitrogen atom or -CR Ｘ１１ = represents. R Ｘ１１ represents a hydrogen atom or a substituent. ａ１１ is X ａ１１ and X ａ１２ represents a ring containing ａ１１ The ring represented by the formula (I) may further have a substituent. In formula (1A-3), * represents a bonding position. ａ１１ and X a13 represents Y in the formula (1A). ａ１１ and X a13. ａ１１ represents a pyrazole ring.

17. Y ａ１１ The compound of claim 16, wherein is an oxygen atom.

18. Ar ａ１１ The compound according to claim 16 or 17, wherein is a five-membered ring.

19. A １ is a group represented by formula (2A) or a group represented by formula (3A). 【Chemistry 10】 In formula (2A), * represents a bonding position. ａ２１ represents a hydrogen atom or a substituent. ａ２１ ~X ａ２３ are each independently a nitrogen atom or —CR Ｘ２１ = represents. R Ｘ２１ represents a hydrogen atom or a substituent. In formula (3A), * represents a bonding position. ａ３１ and R ａ３２ each independently represents a hydrogen atom or a substituent. ａ３１ and X ａ３２ are each independently a nitrogen atom or —CR Ｘ２２ = represents. R Ｘ２２ represents a hydrogen atom or a substituent.

20. D １ is a group represented by any one of formulas (1D) to (3D): 【Chemistry 11】 In formula (1D), * represents a bonding position. ｄ１１ represents an aromatic ring containing two or more carbon atoms. ｄ１１ The aromatic ring represented by R may further have a substituent. ｄ１１ and R ｄ１２ are each independently -C(R Ｌ１１ ) (R Ｌ１２ ) (R Ｌ１３ ) or an aromatic ring group which may have a substituent. Ｌ１１ ~R Ｌ１３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ１１ ~R Ｌ１３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ１３ represents a hydrogen atom or a substituent. In formula (2D), * represents a bonding position. ｄ２１ represents an aromatic ring containing two or more carbon atoms. ｄ２１ The aromatic ring represented by the formula (I) may further have a substituent. ｄ２１ represents a chalcogen atom or -NR Ｚ２１ - represents. Ｚ２１ represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. ｄ２２ is a nitrogen atom or -CR Ｚ２２ = represents. R Ｚ２２ represents a hydrogen atom or a substituent. In formula (3D), * represents a bonding position. ｄ３１ and Ar ｄ３２ each independently represents an aromatic ring containing two or more carbon atoms. ｄ３１ and Ar ｄ３２ The aromatic ring represented by the formula (I) may further have a substituent. ｄ３１ is -CR Ｚ３１ R Ｚ３２ -, -SiR Ｚ３１ R Ｚ３２ - or > C=R Ｚ３３ Represents R Ｚ３１ and R Ｚ３２ R each independently represents a hydrogen atom or a substituent. Ｚ３１ and R Ｚ３２ may be bonded to each other to form a ring. Ｚ３３ represents an oxygen atom, a sulfur atom, or ═CR Ｚ３４ R Ｚ３５ Represents R Ｚ３４ and R Ｚ３５ R each independently represents a hydrogen atom or a substituent. Ｚ３４ and R Ｚ３５ and Ar ｄ３１ and Ar ｄ３２ may be condensed with at least one of R to form a condensed ring. ｄ３１ represents a hydrogen atom or a substituent.

21. D １ is a group represented by formula (1D).

22. D １ The compound according to any one of claims 16 to 21, wherein is a group represented by formula (4D): 【Chemistry 12】 In formula (4D), * represents a bonding position. ｄ４１ and R ｄ４２ are each independently -C(R Ｌ４１ ) (R Ｌ４２ ) (R Ｌ４３ ) or an aromatic ring group which may have a substituent. Ｌ４１ ~R Ｌ４３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ４１ ~R Ｌ４３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ４３ represents a hydrogen atom or a substituent. ｄ４１ ~E ｄ４４ are each independently a nitrogen atom or —CR Ｅ４１ = represents. R Ｅ４１ represents a hydrogen atom or a substituent. Ｅ４１ If there are multiple R Ｅ４１ They may be bonded to each other to form a ring.

23. D １ The compound according to any one of claims 16 to 22, wherein is a group represented by formula (5D): 【Chemistry 13】 In formula (5D), * represents a bonding position. ｄ５１ and R ｄ５２ are each independently -C(R Ｌ５１ ) (R Ｌ５２ ) (R Ｌ５３ ) or an aromatic ring group which may have a substituent. Ｌ５１ ~R Ｌ５３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ５１ ~R Ｌ５３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ５３ ~R ｄ５５ R each independently represents a hydrogen atom or a substituent. ｄ５４ and R ｄ５５ may be bonded to each other to form a ring.

24. D １ The compound according to any one of claims 16 to 23, wherein is a group represented by formula (6D): 【Chemistry 14】 In formula (6D), * represents a bonding position. ｄ６１ and R ｄ６２ are each independently -C(R Ｌ６１ ) (R Ｌ６２ ) (R Ｌ６３ ) or an aromatic ring group which may have a substituent. Ｌ６１ ~R Ｌ６３ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Ｌ６１ ~R Ｌ６３ The optionally substituted alkyl groups or optionally substituted aromatic ring groups represented by the following formula (I) may be bonded to each other to form a ring. ｄ６３ ~R ｄ６５ R each independently represents a hydrogen atom or a substituent. ｄ６４ and R ｄ６５ may be bonded to each other to form a ring. ｄ６１ and E ｄ６２ are each independently a nitrogen atom or —CR Ｅ６１ = represents. R Ｅ６１ represents a hydrogen atom or a substituent.

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