Photoelectric conversion element, imaging element, photosensor, method for producing imaging element, and compound

Abstract

The present invention addresses the problem of providing a photoelectric conversion element demonstrating excellent response speed upon receipt of red light, where the response speed exhibits low dependency on electromagnetic intensity. This photoelectric conversion element has, in the given order, an electroconductive film, a photoelectric conversion film, and a transparent electroconductive film. The photoelectric conversion film contains a compound represented by formula (1).

Description

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

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

[0002] In recent years, development of devices having a photoelectric conversion film (e.g., image pickup devices) has progressed. For example, Non-Patent Document 1 discloses an organic semiconductor compound having a specific structure as a compound applicable to organic solar cells.

[0003] Materials Chemistry Frontiers (2018), 2(12), 2333-2339

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

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

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

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described later. [2] The photoelectric conversion element according to [1], wherein the group represented by formula (2) described later is a group represented by formula (2-1) described later or a group represented by formula (2-2) described later, and the group represented by formula (3) described later is a group represented by formula (3-1) described later or a group represented by formula (3-2) described later. [3] The photoelectric conversion element according to [1] or [2], wherein the group represented by formula (A-1) described later is a group represented by formula (A-3) described later. [4] A １ and A ２ [5] The photoelectric conversion element according to any one of [1] to [3], wherein X is independently a group represented by formula (C-1) or formula (C-2) described later. １ and X ２ But, -NR Ｎ１ - and R Ｎ１ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted aromatic ring group; and in formula (3) described below, X ３ and X ４ But, -NR Ｎ２ - and R Ｎ２ [6] The photoelectric conversion element according to any one of [1] to [4], wherein R represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or an aromatic ring group which may have a substituent. Ｎ１ represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T described below; Ｎ２represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group optionally having a substituent selected from the substituent group T described below. [7] The photoelectric conversion element according to any one of [1] to [6], wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) with the n-type organic semiconductor. [8] The photoelectric conversion element according to [7], wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof. [9] The photoelectric conversion element according to any one of [1] to [8], wherein the photoelectric conversion film further contains a p-type organic semiconductor.

[10] The photoelectric conversion element according to any one of [1] to [9], wherein the photoelectric conversion film further contains a dye.

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

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

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

[11] .

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

[11] .

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

[11] .

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

[16] The compound according to

[15] , wherein the group represented by formula (2) described later is a group represented by formula (2-1) described later or a group represented by formula (2-2) described later, and the group represented by formula (3) described later is a group represented by formula (3-1) described later or a group represented by formula (3-2) described later.

[17] The compound according to

[15] or

[16] , wherein the group represented by formula (A-1) described later is a group represented by formula (A-3). １ and A ２ are each independently a group represented by formula (C-1) or formula (C-2) described later. １ and X ２ But, -NR Ｎ１ - and RＮ１ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted aromatic ring group; and in formula (3) described below, X ３ and X ４ But, -NR Ｎ２ - and R Ｎ２

[20] The compound according to any one of

[15] to

[18] , wherein R represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted aromatic ring group. Ｎ１ represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T described below; Ｎ２ represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T described below.

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

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

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

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] In this specification, a hydrogen atom may be either a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom). In this specification, when there are multiple substituents, linking groups, etc. (hereinafter also referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are specified at the same time, this means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.

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

[0014] (Substituent W) The substituent W in this specification will be described. Examples of the substituent W include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (a heteroaryl group, or an aliphatic heterocyclic group), a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryl ... Examples of the substituent W include an anyloxy group, a primary, secondary, or tertiary amino group (including an anilino group), an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a carboxy group, a phosphate group, a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, and a boronic acid group. Furthermore, each of the above groups may further have a substituent (e.g., one or more of the above groups, etc.), if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. Furthermore, when the substituent W has a carbon atom, the number of carbon atoms contained in the substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30. The specific compounds described below may have, as substituents, a carboxy group, a salt of a carboxy group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) ２ ) and / or does not have a primary amino group.

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

[0016] In this specification, the aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Furthermore, in this specification, unless otherwise specified, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclopropyl group, and a cyclopentyl group. Furthermore, the alkyl group may be a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have these ring structures as partial structures. In the alkyl group that may have a substituent, examples of the substituent that the alkyl group may have include the groups exemplified for the substituent W. Of these, an aryl group (preferably having 6 to 18 carbon atoms, more preferably having 6 carbon atoms), a heteroaryl group (preferably having 5 to 18 carbon atoms, more preferably having 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom) is preferred.

[0017] In this specification, unless otherwise specified, the alkyl group moiety in the alkoxy group is preferably the above-mentioned alkyl group. The alkyl group moiety in the alkylthio group is preferably the above-mentioned alkyl group. In the alkoxy group which may have a substituent, examples of the substituent that the alkoxy group may have include the same as the substituent in the alkyl group which may have a substituent. In the alkylthio group which may have a substituent, examples of the substituent that the alkylthio group may have include the same as the substituent in the alkyl group which may have a substituent.

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

[0019] In this specification, unless otherwise specified, an aromatic ring or an aromatic ring constituting an aromatic ring group may be either a monocyclic ring or a polycyclic ring (e.g., 2 to 6 rings). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure. A polycyclic (e.g., 2 to 6 rings) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6) condensed aromatic ring structures as a ring structure. The number of ring members in the aromatic ring is preferably 5 to 15. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. When the aromatic ring is an aromatic heterocyclic ring, the number of heteroatoms contained as ring member atoms is, for example, 1 to 10. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring.Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (e.g., a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (e.g., a 1,2,4,5-tetrazine ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a naphthopyrrole ring, a naphthofuran ring, a naphthothiophene ring, a naphthoimidazole ring, a naphthoxazole ring, a pyrroloimidazole ring (e.g., a 5H-pyrrolo[1,2-a]imidazole ring), an imidazooxazole ring (e.g., an imidazo[2,1-b]oxazole ring). , thienothiazole rings (for example, thieno[2,3-d]thiazole rings, etc.), benzothiadiazole rings, benzodithiophene rings (for example, benzo[1,2-b:4,5-b']dithiophene rings, etc.), thienothiophene rings (for example, thieno[3,2-b]thiophene rings, etc.), thiazolothiazole rings (for example, thiazolo[5,4-d]thiazole rings, etc.), naphthodithiophene rings (for example, naphtho[2,3 [2,1-b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc.), benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring, and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring.

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

[0021] As used herein, the term "non-aromatic ring" refers to a ring structure that does not fall under the category of aromatic rings, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle. Examples of the aliphatic hydrocarbon ring include a cycloalkane, a cycloalkene, and a cycloalkyne. Examples of the aliphatic heterocycle include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, and a γ-butyrolactone ring. As used herein, the term "aliphatic hydrocarbon ring group" includes, for example, a group obtained by removing one hydrogen atom from a ring that falls under the category of an aliphatic hydrocarbon ring. As used herein, the term "aliphatic heterocyclic group" includes, for example, a group obtained by removing one hydrogen atom from a ring that falls under the category of an aliphatic heterocycle.

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

[0023] In this specification, the bonding direction of a divalent group (e.g., -CO-O-, etc.) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be either "X-O-CO-Z" or "X-CO-O-Z."

[0024] In this specification, with respect to compounds that may have geometric isomers (cis-trans isomers), the general formula or structural formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.

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

[0026] [Photoelectric conversion element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) (hereinafter also referred to as a "specific compound").

[0027] Although the reason why the photoelectric conversion element having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The specific compound is a so-called ADA-type dye compound having a donor portion (D) and an acceptor portion (A). ADA-type dye compounds tend to be highly aggregative due to their conjugated structure. As represented by formula (1), the specific compound has a specific donor directly bonded to the acceptor, thereby appropriately controlling the absorption wavelength to the target wavelength and suppressing excessive aggregation between specific compounds in the photoelectric conversion film, thereby achieving efficient charge separation. As a result, it is believed that a photoelectric conversion element containing the specific compound has excellent response speed and a small electric field strength dependency of the response speed. Hereinafter, achieving at least one of a superior response speed and a small electric field strength dependency of the response speed is also referred to as "excellent effects of the present invention."

[0028] FIG. 1 shows a cross-sectional schematic diagram of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in FIG. 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 functioning as an upper electrode are stacked in this order. FIG. 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in FIG. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be changed as appropriate depending on the application and characteristics.

[0029] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15. When the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 is applied between the pair of electrodes. －５ ~1 x 10 ７ In terms of performance and power consumption, it is preferable to apply a voltage of 1×10 V / cm. －４ ~1 x 10 ７ V / cm is more preferable, and 1×10 －３ ~5 x 10 ６ V / cm is more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an imaging element, a voltage can be applied in a similar manner. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0030] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film.

[0031] <Specific Compound> The photoelectric conversion film contains a specific compound, which is a compound represented by formula (1).

[0032]

[0033] In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. D represents a group represented by formula (2) or a group represented by formula (3). A １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (2), * represents a bonding position. Z １ and Z ２ each independently represents an oxygen atom or a sulfur atom. １ and X ２ are each independently -NRＮ１ represents an oxygen atom, a sulfur atom, or a selenium atom. Ｎ１ represents a hydrogen atom or a substituent. １ and Ar ２ each independently represents an aromatic ring which may have a substituent. In formula (3), * represents a bonding position. Z ３ and Z ４ each independently represents an oxygen atom or a sulfur atom. ３ and X ４ are each independently -NR Ｎ２ represents an oxygen atom, a sulfur atom, or a selenium atom. Ｎ２ represents a hydrogen atom or a substituent. ３ and Ar ４ each independently represents an aromatic ring which may have a substituent. In formula (A-1), * represents a bonding position. C １ represents a ring containing two or more carbon atoms which may have a substituent. １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ２ , or =CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents R Ｗ５ ~R Ｗ７ R each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. In formula (A-2), * represents a bonding position. ｂ１ and R ｂ２ each independently represents a cyano group, —COOR ｂ３ , -COR ｂ４ , -SOR ｂ５ , - or SO ２ R ｂ６ Represents. R ｂ３ ~R ｂ６each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

[0034] In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W. In terms of the effects of the present invention being more excellent, R １ and R ２ is preferably a hydrogen atom.

[0035] In formula (1), D represents a group represented by formula (2) or a group represented by formula (3).

[0036] In formula (2), * represents a bonding position. １ and Ar ２ On a ring member atom of the aromatic ring represented by formula (1), -C (=A １ ) R １ and a group represented by -C(=A ２ ) R ２ This means that there is a bonding position with a group represented by the formula:

[0037] In formula (2), Z １ and Z ２ each independently represents an oxygen atom or a sulfur atom, and preferably an oxygen atom.

[0038] In formula (2), X １ and X ２ are each independently -NR Ｎ１ represents an oxygen atom, a sulfur atom, or a selenium atom. １ and X ２ As the Ｎ１ - or a sulfur atom is preferred, and -NR Ｎ１ - is more preferable.

[0039] R Ｎ１represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified above for the substituent W. More specific examples of the substituent include an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent, and an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent is preferred.

[0040] Examples of the aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups. The linear aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, even more preferably 3 to 6, and particularly preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8, and even more preferably 3 to 6. Examples of the substituent that the aliphatic hydrocarbon group may have include the substituents exemplified for the substituent W described above. Preferably, a substituent selected from the substituent group S described below is selected, more preferably a substituent selected from the substituent group T described below, and more preferably a halogen atom.

[0041] The aromatic ring group, which may have a substituent, may be either a monocyclic or polycyclic ring. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The number of ring members in the aromatic ring group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8. The number of carbon atoms in the aromatic ring group is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 10. Examples of heteroatoms contained in the aromatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred. Examples of the aromatic ring group are as described above, with a phenyl group, a thiophene ring group, a furan ring group, a thiazole ring group, or a pyridine ring group being preferred, with a phenyl group being more preferred. Examples of the substituent that the aromatic ring group may have include the substituents exemplified above for the substituent W, and are preferably a substituent selected from the substituent group S described below, and more preferably a substituent selected from the substituent group T described below. When the aromatic ring group has a substituent, the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

[0042] The number of ring members in the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8. The number of carbon atoms in the aliphatic heterocyclic group is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 10. Examples of heteroatoms contained in the aliphatic heterocyclic group include sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. Examples of the aliphatic heterocyclic group are as described above, with a piperidine ring group being preferred. Examples of substituents that the aliphatic heterocyclic group may have include the substituents exemplified by the substituent W described above, with substituents selected from the substituent group S described below being preferred, and substituents selected from the substituent group T described below being more preferred. When the aliphatic heterocyclic group has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

[0043] The effect of the present invention is more excellent.Ｎ１ is also preferably a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T described below.

[0044] In formula (2), Ar １ and Ar ２ each independently represents an aromatic ring which may have a substituent. The aromatic ring may be either a monocyclic or polycyclic ring, but is preferably a monocyclic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of ring members in the aromatic ring is 3 or more, preferably 5 to 12, and more preferably 5 or 6. The number of ring members in the aromatic ring is determined by the number of carbon atoms, two of which are clearly indicated in the formula, and -C(=A １ ) R １ or a group represented by -C(=A ２ ) R ２ The number includes atoms at the linking position to the group represented by the formula (I). Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring, with a benzene ring being preferred. Examples of heteroatoms contained in the aromatic heterocycle include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a nitrogen atom, a sulfur atom, or an oxygen atom being preferred. Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a tetrazine ring, a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a pyrazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a thienothiophene ring, a thienofuran ring, a thienopyrrole ring, and a furopyrrole ring, and a pyridine ring, a thiophene ring, a furan ring, a thiazole ring, or an oxazole ring is preferred.

[0045] The aromatic ring may have a substituent. Examples of the substituent include the substituents exemplified by the substituent W described above. More specific examples of the substituent include an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, -Si(R Ｓｉ１ ) ３ and a group represented by the formula (I), an acyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, and a cyano group. Ｓｉ１ ) ３ A group represented by the formula (I), an alkoxy group which may have a substituent, or a halogen atom is preferred. When the aromatic ring has a substituent, the number of the substituents is preferably 1 to 3. It is also preferred that the aromatic ring has no substituent.

[0046] The definitions and preferred embodiments of the optionally substituted aliphatic hydrocarbon group, the optionally substituted aromatic ring group, and the optionally substituted aliphatic heterocyclic group, which are exemplified as the substituent that the aromatic ring may have, are as described above in R Ｎ１ The substituents are the same as the aliphatic hydrocarbon groups which may have a substituent, the aromatic ring groups which may have a substituent, and the aliphatic heterocyclic groups which may have a substituent, which are exemplified as the substituents represented by the following formula:

[0047] The above -Si(R Ｓｉ１ ) ３ In the group represented by Ｓｉ１ R each independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. Ｓｉ１ The definitions and preferred embodiments of the optionally substituted aliphatic hydrocarbon group and optionally substituted aromatic ring group are as follows: Ｎ１ The substituents are the same as the aliphatic hydrocarbon groups and aromatic ring groups which may have a substituent, which are exemplified as the substituents represented by -Si(R Ｓｉ１ ) ３ is a group represented by -Si(R Ｓｉ２ ) ３ It is also preferable that RＳｉ１ is a group represented by R Ｓｉ２ It is also preferable that R is a group represented by the following formula: Ｓｉ２ each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the substituent group T described below, or an aromatic ring group which may have a substituent selected from the substituent group T described below.

[0048] The hydrocarbon group contained in the acyl group, which may have a substituent, may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. The aliphatic hydrocarbon group contained in the acyl group may be linear, branched, or cyclic. The number of carbon atoms in the acyl group is preferably 1 to 21, more preferably 2 to 11, even more preferably 2 to 5, and particularly preferably 2 or 3. Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, and a benzoyl group, with an acetyl group or a propionyl group being preferred. Examples of the substituent that the acyl group may have include the substituents exemplified for the substituent W described above. Preferred are substituents selected from the substituent group S described below, and more preferred are substituents selected from the substituent group T described below.

[0049] The alkyl group contained in the alkoxy group which may have a substituent may be linear, branched, or cyclic. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a t-butoxy group, and a cyclopropoxy group. Examples of the substituent which the alkoxy group may have include the substituents exemplified for the substituent W described above. A substituent selected from the substituent group S described below is preferred, a substituent selected from the substituent group T described below is more preferred, and a halogen atom is even more preferred.

[0050] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred.

[0051] In formula (3), * represents a bonding position. ３ and Ar ４ On a ring member atom of the aromatic ring represented by formula (1), -C (=A １ ) R １ and a group represented by -C(=A ２ ) R ２ This means that there is a bonding position with a group represented by the formula:

[0052] In formula (3), Z ３ and Z ４ each independently represents an oxygen atom or a sulfur atom, and preferably an oxygen atom.

[0053] In formula (3), X ３ and X ４ are each independently -NR Ｎ２ represents an oxygen atom, a sulfur atom, or a selenium atom. ３ and X ４ As the Ｎ２ - or a sulfur atom is preferred, and -NR Ｎ２ - is more preferable.

[0054] R Ｎ２ represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified above for the substituent W. Ｎ２ The definition and preferred embodiments of the group represented by the formula (2) are as follows: Ｎ１ It is the same as the group represented by the following formula:

[0055] In formula (3), Ar ３ and Ar ４ each independently represents an aromatic ring which may have a substituent. ３ and Ar ４ The definition and preferred embodiments of the aromatic ring which may have a substituent represented by the formula (2) are as follows: １ and Ar ２ The aromatic ring may have a substituent, and is the same as the aromatic ring represented by the following formula (1).

[0056] In terms of achieving better effects of the present invention, the group represented by formula (2) is preferably a group represented by formula (2-1) or a group represented by formula (2-2). In terms of achieving better effects of the present invention, the group represented by formula (3) is preferably a group represented by formula (3-1) or a group represented by formula (3-2).

[0057]

[0058] In formula (2-1), Y １ ~Y ４ One of them represents -C(*)=, and Y １ ~Y ４ Three of the groups are independently -CR ａ１ = or a nitrogen atom. * represents a bonding position. In terms of the effects of the present invention being more excellent, Y ２ or Y ３ preferably represents -C(*)=, and Y ２ It is more preferable that Y represents -C(*)=. １ ~Y ４ One or more of the following is -CR ａ１ It is preferable that three represent -CR ａ１ It is more preferable that all three represent -CH=.

[0059] In formula (2-1), Y ５ ~Y ８ One of them represents -C(*)=, and Y ５ ~Y ８ Three of the groups are independently -CR ａ１ = or a nitrogen atom. * represents a bonding position. In terms of the effects of the present invention being more excellent, Y ６ or Y ７ preferably represents -C(*)=, and Y ７ It is more preferable that Y represents -C(*)=. ５ ~Y ８ One or more of the following is -CR ａ１ It is preferable that three represent -CR ａ１ It is more preferable that all three represent -CH=.

[0060] R ａ１ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified by the substituent W described above. More specific examples of the substituent include an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, -Si(R Ｓｉ１ ) ３ Examples of the alkyl group include a group represented by the formula: ａ１ The definition and preferred embodiments of the substituent represented by the formula １ and Ar ２ These are the same as the substituents that may be possessed by the aromatic ring represented by R ａ１ The group may be a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or —Si(R Ｓｉ１ ) ３ A group represented by the following formula (I), an alkoxy group which may have a substituent, or a halogen atom is preferred, and a hydrogen atom is more preferred.

[0061] In formula (2-1), X １ , X ２ , Z １ , and Z ２ are X in formula (2), respectively. １ , X ２ , Z １ , and Z ２ is the same as

[0062] In formula (2-2), * represents a bonding position.

[0063] In formula (2-2), X ５ and X ６ one of which is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ３ -, and the other is -CR ａ２ = or a nitrogen atom. In terms of the effects of the present invention being more excellent, X ５ and X ６ one of the groups is a sulfur atom, an oxygen atom, or —NR Ｎ３Preferably, X represents -, and more preferably represents an oxygen atom or a sulfur atom. ５ and X ６ One of them is -CR ａ２ Preferably, X represents -, and more preferably represents -CH=. ７ and X ８ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or —NR Ｎ３ -, and the other is -CR ａ２ = or a nitrogen atom. In terms of the effects of the present invention being more excellent, X ７ and X ８ one of the groups is a sulfur atom, an oxygen atom, or —NR Ｎ３ Preferably, X represents -, and more preferably represents an oxygen atom or a sulfur atom. ７ and X ８ One of them is -CR ａ２ Preferably, X represents -, and more preferably represents -CH=. ５ and X ７ is a sulfur atom, an oxygen atom, a selenium atom, or —NR Ｎ３ represents -, and X ６ and X ８ Ga-CR ａ２ It is also preferred that ═ represents a nitrogen atom.

[0064] R ａ２ and R Ｎ３ R each independently represents a hydrogen atom or a substituent. ａ２ The definition and preferred embodiments of the group represented by the formula (2-1) are as follows: ａ１ is the same as the group represented by R Ｎ３ The definition and preferred embodiments of the group represented by the formula (2) are as follows: Ｎ１ It is the same as the group represented by the following formula:

[0065] In formula (2-2), X １ , X ２ , Z １ , and Z ２ are X in formula (2), respectively. １ , X ２ , Z １ , and Z ２ is the same as

[0066] In formula (3-1), Y ９ ~Y １２ One of them represents -C(*)=, and Y ９ ~Y １２ Three of the groups are independently -CR ａ３ = or a nitrogen atom. * represents a bonding position. In terms of the effects of the present invention being more excellent, Y １０ or Y １１ preferably represents -C(*)=, and Y １０ It is more preferable that Y represents -C(*)=. ９ ~Y １２ One or more of the following is -CR ａ３ It is preferable that three represent -CR ａ１ It is more preferable that all three represent -CH=.

[0067] In formula (3-1), Y １３ ~Y １６ One of them represents -C(*)=, and Y １３ ~Y １６ Three of the groups are independently -CR ａ３ = or a nitrogen atom. * represents a bonding position. In terms of the effects of the present invention being more excellent, Y １４ or Y １５ preferably represents -C(*)=, and Y １５ It is more preferable that Y represents -C(*)=. １３ ~Y １６ One or more of the following is -CR ａ３ It is preferable that three represent -CR ａ３ It is more preferable that all three represent -CH=.

[0068] R ａ３ represents a hydrogen atom or a substituent. ａ３ The definition and preferred embodiments of the group represented by the formula (2-1) are as follows: ａ１ It is the same as the group represented by the following formula:

[0069] In formula (3-1), X ３ , X ４ , Z ３ , and Z ４are X in formula (3), respectively. ３ , X ４ , Z ３ , and Z ４ is the same as

[0070] In formula (3-2), * represents a bonding position.

[0071] In formula (3-2), X ９ and X １０ one of which is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ４ -, and the other is -CR ａ４ = or a nitrogen atom. In terms of the effects of the present invention being more excellent, X ９ and X １０ one of the groups is a sulfur atom, an oxygen atom, or —NR Ｎ４ Preferably, X represents -, and more preferably represents an oxygen atom or a sulfur atom. ９ and X １０ One of them is -CR ａ４ Preferably, X represents -, and more preferably represents -CH=. １１ and X １２ one of which is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ４ -, and the other is -CR ａ４ = or a nitrogen atom. In terms of the effects of the present invention being more excellent, X １１ and X １２ one of the groups is a sulfur atom, an oxygen atom, or —NR Ｎ４ Preferably, X represents -, and more preferably represents an oxygen atom or a sulfur atom. １１ and X １２ One of them is -CR ａ４ Preferably, X represents -, and more preferably represents -CH=. ９ and X １１ is a sulfur atom, an oxygen atom, a selenium atom, or —NR Ｎ４ represents -, and X １０ and X １２ Ga-CR ａ４ It is also preferred that ═ represents a nitrogen atom.

[0072] R ａ４ and R Ｎ４R each independently represents a hydrogen atom or a substituent. ａ４ and R Ｎ４ The definition and preferred embodiments of the group represented by the formula (2-2) are respectively ａ２ and R Ｎ３ It is the same as the group represented by the following formula:

[0073] In formula (3-2), X ３ , X ４ , Z ３ , and Z ４ are X in formula (3), respectively. ３ , X ４ , Z ３ , and Z ４ is the same as

[0074] Substituent group S and substituent group T are described in detail below. Substituent group S: linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, acyl groups having 1 to 20 carbon atoms, aliphatic heterocyclic groups which may have a substituent, aromatic ring groups which may have a substituent, halogen atoms, and -Si(R Ｓｉ３ ) ３ In the above Substituent Group S, the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms (hereinafter also referred to as "aliphatic hydrocarbon groups in Substituent Group S"), as well as the acyl group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms, may have a halogen atom.

[0075] The number of carbon atoms in the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms in the above substituent group S is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The number of carbon atoms in the branched aliphatic hydrocarbon group having 3 to 20 carbon atoms in the above substituent group S is preferably 3 to 10, more preferably 3 to 6, and even more preferably 3 or 4. The cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms in the above substituent group S may be either monocyclic or polycyclic, and preferably monocyclic. The number of carbon atoms in the above cyclic aliphatic hydrocarbon group is preferably 3 to 10, more preferably 3 to 8, even more preferably 3 to 6, and particularly preferably 3.

[0076] The alkyl group contained in the alkoxy group having 1 to 20 carbon atoms in the above-mentioned Substituent Group S may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. The hydrocarbon group contained in the acyl group having 1 to 20 carbon atoms in the above-mentioned Substituent Group S may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The number of carbon atoms in the above-mentioned acyl group is preferably 1 to 10, more preferably 2 to 5, and still more preferably 2 to 4.

[0077] Examples of halogen atoms that may be contained in the aliphatic hydrocarbon group, the acyl group having 1 to 20 carbon atoms, and the alkoxy group having 1 to 20 carbon atoms in the above-mentioned substituent group S include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred. The number of halogen atoms that may be contained in the aliphatic hydrocarbon group, the acyl group having 1 to 20 carbon atoms, and the alkoxy group having 1 to 20 carbon atoms in the above-mentioned substituent group S is not particularly limited, and for example, the aliphatic hydrocarbon group in the above-mentioned substituent group S may be a perfluoroalkyl group.

[0078] The aromatic ring group in the substituent group S may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The number of ring members in the aromatic ring group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8. Specific examples of the aromatic ring group are as described above, with a phenyl group being preferred. As the substituent that the aromatic ring group may have, a substituent selected from the substituent group S is preferred, and a substituent selected from the substituent group T described below is more preferred. When the aromatic ring group has a substituent, the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

[0079] The aliphatic heterocyclic group in the substituent group S may be either a monocycle or a polycycle, with a monocycle being preferred. The number of ring members in the aliphatic heterocyclic group is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 8. The number of carbon atoms in the aliphatic heteroatom is preferably 2 to 20, more preferably 2 to 10, and even more preferably 3 to 6. Specific examples of the aliphatic heterocyclic group are as described above, with a piperidine ring being preferred. As the substituent that the aliphatic heterocyclic group may have, a substituent selected from the substituent group S is preferred, and a substituent selected from the substituent group T described below is more preferred. When the aliphatic heterocyclic group has a substituent, the number of the substituent is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

[0080] Examples of the halogen atom in the above-mentioned substituent group S include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0081] -Si(R Ｓｉ３ ) ３ In the group represented by Ｓｉ３ R represents a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic ring group which may have a substituent. Ｓｉ３ The definitions and preferred embodiments of each group represented by the following formula are the same as those of each group in the substituent group S.

[0082] The substituents selected from the substituent group S are preferably those selected from the substituent group T, in that the effects of the present invention are more excellent. The substituents from the substituent group T include linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, aliphatic heterocyclic groups having 3 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 3 carbon atoms, and -Si(R Ｓｉ４ ) ３ A group represented by R Ｓｉ４represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, or an aromatic ring group which may have a substituent selected from Substituent Group T.

[0083] In formula (1), A １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). １ and A ２ is preferably a group represented by formula (C-1) described below or a group represented by formula (C-2) described below.

[0084]

[0085] In formula (A-1), * represents a bonding position.

[0086] In formula (A-1), C １ represents a ring containing two or more carbon atoms which may have a substituent. １ The two carbon atoms contained in are the two carbon atoms specified in formula (A-1). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the two carbon atoms specified in the formula. The ring may be either an aromatic ring or a non-aromatic ring. The ring may be either a monocyclic or polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms in the ring is preferably 0 to 10, and more preferably 0 to 5. １ Among the carbon atoms constituting the ring represented by the formula (A-1), the carbon atom at the bonding position marked with * and W １Carbon atoms other than the carbon atom bonded to may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0087] Above C １ Examples of the substituent that the ring represented by the formula (I) may have include the groups exemplified for the substituent W above, and a halogen atom, an alkyl group, an aromatic ring group, a cyano group, or a silyl group is preferred, with a halogen atom or an alkyl group being more preferred. The alkyl group may be linear, branched, or cyclic, with a linear group being preferred. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0088] Above C １The ring represented by the formula (I) is preferably a ring used as an acidic nucleus (for example, the acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, a 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione; (b) pyrazolinone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one; (c) isoxazolinone nucleus: for example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one; (d) oxindole nucleus: for example, 1-alkyl-2,3-dihydro-2-oxindole; (e) 2,4,6-trioxohexahydropyrimidine nucleus: for example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl, and 1,3-dibutyl, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl), and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl). (f) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-heteroarylrhodanines such as 3-(2-pyridyl)rhodanine. (g) 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazoledione nucleus): for example, 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone nucleus: for example, 3(2H)-thianaphthenone-1,1-dioxide. (i) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione.(j) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione. (k) thiazolin-4-one nucleus: for example, 4-thiazolinone and 2-ethyl-4-thiazolinone. (l) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione. (n) Imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one, etc. (o) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione, etc. (p) Benzothiophen-3(2H)-one nucleus: for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one, etc. (q) Indanone nucleus: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone, etc. (r) Benzofuran-3-(2H)-one nucleus: for example, benzofuran-3-(2H)-one, etc. (s) 2,2-dihydrophenalene-1,3-dione nucleus, etc.

[0089] In formula (A-1), W １ represents an oxygen atom, a sulfur atom, and ═NR Ｗ２ , or =CR Ｗ３ R Ｗ４ Represents W. １ is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom, in that the effects of the present invention are more excellent. Ｗ２ represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified above as the substituent W. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -CORＷ７ Represents R Ｗ５ ~R Ｗ７ R each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. The aliphatic hydrocarbon group is defined as above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The aromatic ring group is defined as above, and an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. The aliphatic heterocyclic group is defined as above, and the heteroatom contained in the aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. R Ｗ５ ~R Ｗ７ Examples of the substituent that each group represented by the following formula may have include the substituents exemplified for the substituent W above.

[0090] The group represented by formula (A-1) is preferably a group represented by formula (A-3) in that the effects of the present invention are more excellent.

[0091]

[0092] In formula (A-3), * represents a bonding position.

[0093] In formula (A-3), C ２ represents a ring containing at least three carbon atoms, which may have a substituent. ２The three carbon atoms contained in are the three carbon atoms specified in formula (A-3). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the three carbon atoms specified in the formula. The ring may be either an aromatic ring or a non-aromatic ring. The ring may be either a monocyclic or polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The ring may have a heteroatom. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5. ２ Among the carbon atoms constituting the ring represented by the formula (A-3), the carbon atom at the bonding position marked with * and Y ２ or Y ３ The carbon atoms other than the carbon atom bonded to the ring may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S). １ The substituents are the same as those that the ring represented by the formula (I) may have.

[0094] In formula (A-3), W ２ and W ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or =CR Ｗ３ R Ｗ４ Represents W. ２ and W ３ As R, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred, in terms of better effects of the present invention. Ｗ２ ~R Ｗ４ is as described above.

[0095] The group represented by formula (A-3) is more preferably a group represented by formula (C-1) or a group represented by formula (C-2) in that the effects of the present invention are more excellent.

[0096]

[0097] In formula (C-1), * represents a bonding position.

[0098] In formula (C-1), X ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or =CR Ｗ３ R Ｗ４ The effect of the present invention is more excellent, and therefore, X ｃ１ and X ｃ２ is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. ｃ１ and X ｃ２ is preferably an oxygen atom, and X ｃ１ and X ｃ２ It is more preferable that R is an oxygen atom. Ｗ２ ~R Ｗ４ is as described above.

[0099] In formula (C-1), C ３ represents an aromatic ring which may have a substituent. The aromatic ring may be either a monocyclic or polycyclic ring. The number of ring members in the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of ring members in the aromatic ring is the number including the two carbon atoms specified in the formula. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and an aromatic hydrocarbon ring is preferred. The above C ３The aromatic ring represented by the formula (I) is as described above, and is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyridine ring, a thienothiophene ring, a benzothiophene ring, a benzofuran ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring, more preferably a benzene ring, a naphthalene ring, or a thiophene ring, and even more preferably a benzene ring. Examples of the substituent that the aromatic ring may have include the groups exemplified by the substituent W, and an alkyl group or a halogen atom is preferred. The number of substituents that the aromatic ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.

[0100] In formula (C-2), * represents a bonding position.

[0101] In formula (C-2), X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or =CR Ｗ３ R Ｗ４ The effect of the present invention is more excellent, and therefore, X ｃ３ ~X ｃ５ is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. ｃ３ and X ｃ４ is preferably an oxygen atom, and X ｃ３ ~X ｃ５ It is more preferable that R is an oxygen atom. Ｗ２ ~R Ｗ４ is as described above.

[0102] In formula (C-2), R ｃ１ and R ｃ２each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified by the substituent W above, with an alkyl group or an aryl group being preferred, and an alkyl group being more preferred. The alkyl group may be linear, branched, or cyclic, with a linear group being preferred. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The aryl group may be monocyclic or polycyclic, with a phenyl group being preferred. The aryl group may further have a substituent, and examples of the substituent include the groups exemplified by the substituent W above.

[0103] In formula (A-2), * represents a bonding position. ｂ１ and R ｂ２ each independently represents a cyano group, —COOR ｂ３ , -COR ｂ４ , -SOR ｂ５ , or -SO ２ R ｂ６ represents a cyano group, -COOR ｂ３ , -COR ｂ４ or a cyano group is preferred, and a cyano group is more preferred. ｂ１ and R ｂ２ It is also preferred that at least one of R is a cyano group. ｂ３ ~R ｂ６ R each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. The aliphatic hydrocarbon group is defined as above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The aromatic ring group is defined as above, and an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. The aliphatic heterocyclic group is defined as above, and the heteroatom contained in the aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. R ｂ３ ~R ｂ６ Examples of the substituent that each group represented by the formula (I) may have include the substituents exemplified for the substituent W above, and a halogen atom, an alkyl group, or an aryl group is preferred.

[0104] Examples of specific compounds are shown below, but are not limited to these.

[0105]

[0106]

[0107]

[0108] In the specific compounds exemplified above, A represents any of the following groups: In addition, two A's present in the specific compounds exemplified above may be the same or different.

[0109]

[0110]

[0111]

[0112]

[0113] The molecular weight of the specific compound is preferably 400 to 1000, more preferably 400 to 900, and even more preferably 400 to 800. When the molecular weight is within the above range, the sublimation temperature of the specific compound is lowered, and it is presumed that the specific compound has excellent suitability for production.

[0114] The specific compound preferably has an ionization potential of −5.0 to −6.0 eV in a single film from the viewpoints of stability when used as a p-type organic semiconductor and matching of the energy level with an n-type organic semiconductor.

[0115] The maximum absorption wavelength of the specific compound is preferably in the wavelength range of 450 to 800 nm, more preferably in the range of 500 to 800 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the specific compound is insoluble in chloroform, the maximum absorption wavelength of the specific compound is determined by evaporating the specific compound and measuring the value using the specific compound in a film state.

[0116] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, an optical sensor, or a photovoltaic cell. The specific compound often functions as a dye in the photoelectric conversion film. The specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.

[0117] The specific compound may be purified as necessary. Examples of methods for purifying the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.

[0118] The content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound in terms of a single layer / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75% by volume, more preferably 10 to 50% by volume, and even more preferably 15 to 40% by volume. Only one type of specific compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.

[0119] <n-Type Organic Semiconductor> The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the specific compound. The n-type organic semiconductor is a compound different from the specific compound. The n-type organic semiconductor is an acceptor organic semiconductor material (compound) and refers to an organic compound that has the property of easily accepting electrons. In other words, the n-type organic semiconductor refers to the organic compound that has a larger electron affinity when two organic compounds are used in contact with each other. In other words, any organic compound can be used as the acceptor organic semiconductor as long as it is an organic compound with electron-accepting properties. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; fused aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole). ), polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic diimide derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; 3,4,9,10-perylenetetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic diimide derivatives; and the compounds described in paragraphs

[0056] to

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

[0120] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred. For example, fullerene C ６０ , fullerene C ７０, fullerene C ７６ , fullerene C ７８ , fullerene C ８０ , fullerene C ８２ , fullerene C ８４ , fullerene C ９０ , fullerene C ９６ , fullerene C ２４０ , fullerene C ５４０ and mixed fullerenes. Examples of fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerenes. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. Preferred fullerene derivatives are the compounds described in JP-A-2007-123707.

[0121] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0122] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or in the range of more than 400 nm to 600 nm.

[0123] The photoelectric conversion film preferably has a bulk heterostructure formed in a state in which a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in the photoelectric conversion film in which a specific compound and an 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.

[0124] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0125] When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (thickness of the n-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.

[0126] When the n-type organic semiconductor contains fullerenes, the content of the fullerenes relative to the total content of the n-type organic semiconductors (film thickness of fullerenes converted into a single layer / total film thickness of each n-type organic semiconductor converted into a single layer × 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. Fullerenes may be used singly or in combination of two or more types.

[0127] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor) x 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume. When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the p-type organic semiconductor) x 100) is preferably 10 to 75% by volume, more preferably 15 to 50% by volume. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and a p-type organic semiconductor that is included as desired. "Substantially" means that the total content of the specific compound, n-type organic semiconductor, and p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume.

[0128] <p-Type Organic Semiconductor> The photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the specific compound. The p-type organic semiconductor is a compound different from the specific compound. The p-type organic semiconductor is a donor organic semiconductor material (compound) and refers to an organic compound that has the property of easily donating electrons. In other words, the p-type organic semiconductor refers to the organic compound that has a smaller ionization potential when two organic compounds are used in contact with each other. The p-type organic semiconductor may be used alone or in combination of two or more types.

[0129] Examples of p-type organic semiconductors include triarylamine compounds (e.g., N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), compounds described in paragraphs

[0128] to

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

[0052] to

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

[0119] to

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

[0044] to

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

[0086] to

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

[0031] to

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

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

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

[0015] to

[0025] of WO2018 / 207722,

[0045] to

[0053] , compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

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

[0044] to

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

[0041] to

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

[0034] to

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

[0033] to

[0036] of JP-A No. 2018-206878, the compounds of paragraphs

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

[0019] to

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

[0031] to

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

[0036] to

[0041] of JP-A No. 2018-166200

[0055] to

[0082] compounds, the compounds of paragraphs

[0041] to

[0050] of JP-A-2018-113425, the compounds of paragraphs

[0044] to

[0048] of JP-A-2018-085430, the compounds of paragraphs

[0041] to

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

[0042] to

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

[0031] to

[0036] of JP-A-2018-014474 ] compounds, WO2018 / 016465 paragraphs

[0036] to

[0046] compounds described in, as well as JP-A-2020-010024 paragraphs

[0045] to

[0048] compounds, etc.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. Examples of p-type organic semiconductors include benzoxazole compounds (for example, compounds described in Figures 3 to 7 of JP-A No. 2022-123944), dicarbazole compounds (for example, compounds described in Figures 2 to 5 of JP-A No. 2022-122839), benzoquinazoline compounds (for example, compounds described in paragraphs

[0053] to

[0056] of JP-A No. 2022-120323), and azine compounds (for example,compounds described in paragraphs

[0041] to

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

[0065] to

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

[0052] to

[0073] of JP-A No. 2023-005703, Examples of p-type organic semiconductors include compounds having a lower ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are listed below.

[0130]

[0131]

[0132]

[0133]

[0134] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0135] When the photoelectric conversion film contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the photoelectric conversion film (thickness of the p-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.

[0136] The photoelectric conversion film containing the specific compound is a non-luminescent film and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode). A non-luminescent film means a film having a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less. The lower limit is often 0% or more.

[0137] <Dye> The photoelectric conversion film preferably contains a dye in addition to the specific compound. The dye is a compound different from the specific compound. The dye is preferably an organic dye. Examples of the organic dye include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, and acrylonitrile dyes. Examples of the organic dye include lysinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, imidazoquinoxaline dyes described in WO 2020 / 013246, WO 2022 / 168856, JP 2023-010305 A, and JP 2023-010299 A, as well as acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and donor-acceptor-donor type dyes in which two donors are bonded to an acceptor. Among these, cyanine dyes, imidazoquinoxaline dyes, and acceptor-donor-acceptor type dyes are preferred as organic dyes.

[0138] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and even more preferably in the wavelength range of 450 to 650 nm.

[0139] The content of the dye relative to the total content of the specific compound and the dye in the photoelectric conversion film (= (film thickness of the dye in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the dye in terms of a single layer)×100)) is preferably 5 to 75 vol%, more preferably 5 to 60 vol%, and still more preferably 5 to 50 vol%.

[0140] <Film formation method> Examples of the film formation method for the photoelectric conversion film include dry film formation methods. Examples of dry film formation methods include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and vacuum deposition methods are preferred. When forming the photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0141] The thickness of the photoelectric conversion film is preferably from 10 to 1,000 nm, more preferably from 50 to 800 nm, and even more preferably from 50 to 500 nm.

[0142] [Electrodes] The photoelectric conversion element preferably has electrodes. The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of conductive materials include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident through the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and nanocarbon materials such as carbon nanotubes and graphene. Of these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0143] Typically, when the conductive film is made thinner than a certain range, the resistance value often increases rapidly. In a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10,000 Ω / □, and there is a wide degree of freedom in the range of film thickness that can be reduced. Furthermore, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher the light transmittance. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and enhances photoelectric conversion performance. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance that accompany a reduction in film thickness, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0144] Depending on the application, the lower electrode 11 may be made transparent or may be made non-transparent and reflect light. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.

[0145] The method for forming the electrodes can be appropriately selected depending on the electrode material. Specific examples include wet methods such as printing and coating; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD. When the electrode material is ITO, examples include electron beam methods, sputtering, resistance heating deposition, chemical reaction methods (such as the sol-gel method), and coating of a dispersion of indium tin oxide.

[0146] [Charge-blocking film: electron-blocking film, hole-blocking film] The photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge-blocking film. When the photoelectric conversion element has this film, the properties (quantum efficiency, response speed, etc.) of the resulting photoelectric conversion element are more excellent. Examples of the charge-blocking film include an electron-blocking film and a hole-blocking film.

[0147] <Electron Blocking Film> The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Polymer materials can also be used as the electron blocking film. Examples of polymer materials include polymers of phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, as well as derivatives thereof.

[0148] The electron blocking film may be composed of multiple films. The electron blocking film may be composed of an inorganic material. In general, inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency. Examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0149] <Hole-Blocking Film> The hole-blocking film is an acceptor organic semiconductor material (compound), and the n-type organic semiconductors described above can be used. The hole-blocking film may be composed of multiple films.

[0150] Examples of methods for producing a charge blocking film include dry film formation and wet film formation. Examples of dry film formation methods include vapor deposition and sputtering. Vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition such as vacuum deposition being preferred. Examples of wet film formation methods include inkjet printing, spray printing, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with the inkjet method being preferred in terms of high-precision patterning.

[0151] The thickness of each of the charge blocking films (electron blocking film and hole blocking film) is preferably from 3 to 200 nm, more preferably from 5 to 100 nm, and even more preferably from 5 to 30 nm.

[0152] [Substrate] The photoelectric conversion element may further include a substrate. Examples of the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate. The substrate is usually positioned such that a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked in this order on the substrate.

[0153] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. The performance of photoelectric conversion materials may be significantly degraded in the presence of degrading factors such as water molecules. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of ceramics such as dense metal oxides, metal nitrides, or metal nitride oxides, or diamond-like carbon (DLC), which do not allow water molecules to penetrate. Examples of sealing layers include those described in paragraphs

[0210] to

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

[0154] [Method for manufacturing photoelectric conversion element] Examples of methods for manufacturing photoelectric conversion elements include known manufacturing methods. Specifically, for example, methods for manufacturing photoelectric conversion elements include a step of forming a conductive film on a substrate, a step of forming a photoelectric conversion film, and a step of forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer) in addition to the above. The method for forming each layer is as described above.

[0155] [Imaging element] An example of an application of a photoelectric conversion element is an imaging element. An imaging element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal and outputting the electrical signal pixel by pixel from the imaging element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The manufacturing method of an imaging element is not particularly limited, but examples include a method including the step of manufacturing the photoelectric conversion element described above.

[0156] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, a photocell and an optical sensor, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged linearly or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.

[0157] [Compound] The present invention also includes inventions of specific compounds.

[0158] 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.

[0159] [Compounds used in photoelectric conversion film] The materials used in the photoelectric conversion film are shown below.

[0160] [Synthesis of Compound (1-1)] Compound (1-1) was synthesized according to the following scheme.

[0161]

[0162] <Synthesis of Intermediate (1-1-2)> 7.9 mmol of compound (1-1-1), 32 mmol of 2-iodopropane, 40 mmol of potassium carbonate, and 50 mL of N,N-dimethylformamide were placed in a glass reaction vessel and reacted at 100°C for 12 hours under a nitrogen atmosphere. After cooling, water was added and the solid was filtered off. The resulting solid was purified by silica gel column chromatography to obtain 5.5 mmol of intermediate (1-1-2) (yield 61%).

[0163] <Synthesis of Intermediate (1-1-3)> 5.0 mmol of Intermediate (1-1-2), 15 mmol of N-formylsaccharin, 15 mmol of sodium carbonate, 0.30 mmol of palladium (II) acetate, and 0.45 mmol of 1,4-bis(diphenylphosphino)butane were placed in a glass reaction vessel, and the atmosphere inside the vessel was replaced with nitrogen. 20 mL of N,N-dimethylformamide and 13 mmol of triethylsilane were added, and the reaction was carried out at 75°C for 12 hours. After cooling, water was added, and the solid was collected by filtration. The obtained solid was purified by silica gel column chromatography to obtain 1.5 mmol of Intermediate (1-1-3) (yield 30%).

[0164] <Synthesis of Compound (1-1)> 2.0 mmol of intermediate (1-1-3), 5.0 mmol of 1,3-dimethylbarbituric acid, 60 mL of toluene, and 0.4 mmol of piperidine were placed in a glass reaction vessel and reacted at 100°C for 2 hours under a nitrogen atmosphere. The precipitated solid was collected by filtration, and the resulting solid was washed successively with tetrahydrofuran (THF), N,N-dimethylacetamide, and THF, followed by purification by sublimation to obtain 1.1 mmol of compound (1-1) (yield: 55%). The structure of compound (1-1) was confirmed by LDI-MS (laser desorption ionization mass spectrometry). The results of LDI-MS measurement of compound (1-1) are shown below. LDI-MS (compound (1-1)): 678 (M+)

[0165] The compounds used in the photoelectric conversion film of each of the Examples and Comparative Examples other than the compound (1-1) were synthesized according to the synthesis method of the compound (1-1).

[0166] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for comparison are shown below. Note that compounds (1-1) to (1-6), compound (2-1), compounds (3-1) to (3-3), compounds (4-1), and compounds (5-1) to (5-5) are specific compounds, and compounds (C-1) and (C-2) are comparative compounds.

[0167]

[0168]

[0169] [n-type organic semiconductor] C60: fullerene (C ６０ )

[0170] [p-type organic semiconductor]

[0171]

[0172] [Evaluation] The quantum efficiency, response speed, and electric field intensity dependency of the response speed when the photoelectric conversion element received red light (wavelength 650 nm) were evaluated by the following methods.

[0173] [Fabrication of Photoelectric Conversion Element] A photoelectric conversion element having the configuration shown in FIG. 2 was fabricated using the various components shown above. Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Subsequently, with the glass substrate at room temperature, each specific compound or each comparative compound shown in Table 1 and an n-type organic semiconductor (fullerene (C ６０)) and a p-type organic semiconductor (compound (P-1)) were co-deposited by vacuum deposition to form a film having a thickness of 80 nm in terms of a single layer. This formed a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. At this time, the film formation rate of the photoelectric conversion film 12 was 1.0 Å / sec. Furthermore, compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After a SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al ２ O ３ The resulting laminate was heated in a glove box at 150° C. for 30 minutes to obtain a photoelectric conversion element.

[0174]

[0175] [Dark Current] The dark current of each of the obtained photoelectric conversion elements was measured by the following method. ５ A voltage was applied to the photoelectric conversion element so as to obtain an electric field strength of 50 nA / cm. The current value in a dark place (dark current) was measured. As a result, the dark current was 50 nA / cm for all the photoelectric conversion elements. ２ It was confirmed that the dark current was sufficiently low.

[0176] [Quantum Efficiency] The quantum efficiency of each photoelectric conversion element was measured when red light was received by the following method. ５ After applying a voltage to achieve an electric field strength of 1000 V / cm, light was irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 650 nm, and the quantum efficiency (relative ratio) was calculated according to formula (S1). From the obtained value, the quantum efficiency was evaluated according to the following evaluation criteria. The quantum efficiency is preferably rated C or higher. Formula (S1): Quantum efficiency (relative ratio) = (photoelectric conversion efficiency of each photoelectric conversion element) / (photoelectric conversion efficiency of the photoelectric conversion element of Example 12)

[0177] A: Quantum efficiency (relative ratio) is 1.4 or more. B: Quantum efficiency (relative ratio) is 1.2 or more and less than 1.4. C: Quantum efficiency (relative ratio) is 1.0 or more and less than 1.2. D: Quantum efficiency (relative ratio) is less than 1.0.

[0178] [Response Speed] The response speed of each photoelectric conversion element when receiving red light was evaluated by the following method. ５ A voltage was applied so as to achieve an electric field strength of 1000 V / cm. Thereafter, an LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 650 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity, and the relative response speed was calculated according to formula (S2). From the obtained value, the response speed was evaluated according to the following evaluation criteria. The response speed is preferably evaluated as C or higher. Formula (S2): Relative response speed = (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element of Example 12)

[0179] A: Relative response speed is less than 0.5 B: Relative response speed is 0.5 or more and less than 1.0 C: Relative response speed is 1.0 or more and less than 2.0 D: Relative response speed is 2.0 or more

[0180] [Dependence of response speed on electric field strength] The dependence of the response speed on electric field strength when red light was received was evaluated for each photoelectric conversion element by the following method. In the evaluation of the response speed, a voltage of 7.5×10 was applied to each photoelectric conversion element. ４ The same procedure was followed except that the pressure was changed to 7.5 × 10 ４ The rise time at 7.5 V / cm was measured. The electric field strength dependency of the response speed was calculated according to formula (S3), and the electric field strength dependency of the response speed was evaluated according to the following evaluation criteria. In formula (S3), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. The electric field strength dependency of the response speed is preferably rated C or higher. Formula (S3): Electric field strength dependency of response speed = (applied voltage of each photoelectric conversion element 7.5 × 10 ４ V / cm) / (applied voltage of each photoelectric conversion element 2.0×10５ (rise time in V / cm)

[0181] A: The electric field strength dependency of the response speed is less than 2.5. B: The electric field strength dependency of the response speed is 2.5 or more and less than 3.5. C: The electric field strength dependency of the response speed is 3.5 or more and less than 4.5. D: The electric field strength dependency of the response speed is 4.5 or more.

[0182] [result]

[0183] The evaluation results are shown in Table 1 below. In the table, the column "Formula (1)" indicates "A" when the photoelectric conversion film contains a compound represented by formula (1), and "B" when other cases are not mentioned above. In the table, the column "D" indicates "(2-1)" when D is a group represented by formula (2-1), "(2-2)" when D is a group represented by formula (2-2), "(3-1)" when D is a group represented by formula (3-1), and "(3-2)" when D is a group represented by formula (3-2). In the table, the column "Formula (A-3)" indicates "A" when A is a group represented by formula (2-1), "(2-2)" when D is a group represented by formula (2-2), "(3-1)" when D is a group represented by formula (3-2). １ and A ２ is a group represented by formula (A-3), it is marked as "A", and in other cases it is marked as "B". １ and A ２ is a group represented by formula (C-1) or a group represented by formula (C-2), it is designated as "A", and in other cases it is designated as "B". Ｎ (1)" column indicates the specific compound, X １ and X ２ But, -NR Ｎ１ - and X ３ and X ４ But, -NR Ｎ２ - and R Ｎ１ and R Ｎ２ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or an aromatic ring group which may have a substituent, the group is designated as "A", and the other cases are designated as "B". Ｎ (2)" column indicates the specific compound, R Ｎ１ and R Ｎ２is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T, the group is designated as "A", and other cases are designated as "B".

[0184] In Comparative Example 2, during the procedure of [Fabrication of Photoelectric Conversion Element], the compound decomposed at the stage of forming a film containing the comparative compound (C-2) by co-evaporation, and a photoelectric conversion element could not be fabricated.

[0185]

[0186] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention has an excellent response speed when receiving red light and has a small dependency of the response speed on the electric field strength. It was also confirmed that the photoelectric conversion element of the present invention has an excellent quantum efficiency when receiving red light.

[0187] From a comparison between Example 5 and other Examples, R Ｎ１ and R Ｎ２ is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T. It was confirmed that the dependence of the response speed on the electric field strength is smaller, and the quantum efficiency and response speed are more excellent. １ ~Y ４ Three of them are -CR ａ１ =, and Y ５ ~Y ８ Three of them are -CR ａ１ In formula (2-2), X ５ and X ６ One of them is -CR ａ２ =, and X ７ and X ８ One of them is -CR ａ２ In formula (3-1), Y ９ ~Y １２ Three of them are -CR ａ３ =, and Y １３ ~Y １６ Three of them are -CR ａ３In formula (3-2), X ９ and X １０ One of them is -CR ａ４ =, and X １１ and X １２ One of them is -CR ａ４ It was confirmed that when A = , the dependence of the response speed on the electric field strength was smaller, and the quantum efficiency and response speed were better. １ and A ２ is a group represented by formula (A-3), the quantum efficiency is superior, and when it is a group represented by formula (C-1) or a group represented by formula (C-2), the electric field strength dependency of the response speed is smaller, and the quantum efficiency and response speed are further superior.

[0188] Any of the compounds (1-1), (2-1), (3-1), (4-1), and (5-1), any of the dyes (B-1) to (B-9), and an n-type organic semiconductor (fullerene (C ６０ )) and a p-type organic semiconductor (compound (P-1)), a photoelectric conversion film was formed by depositing a single layer of each of the specific compound, dye, n-type organic semiconductor, and p-type organic semiconductor in a ratio of 1:1:2:2 (converted to thickness). The remaining steps were the same as in the preparation of the photoelectric conversion element described above, and each of the evaluations described above was carried out. Note that for all combinations of each specific compound and dye, photoelectric conversion elements were prepared and each evaluation was carried out. As a result, even when a dye was used in combination, when compound (1-1) was used, the same results as in the example using compound (1-1) shown in Table 1 were obtained, when compound (2-1) was used, the same results as in the example using compound (2-1) shown in Table 1 were obtained, when compound (3-1) was used, the same results as in the example using compound (3-1) shown in Table 1 were obtained, when compound (4-1) was used, the same results as in the example using compound (4-1) shown in Table 1 were obtained, and when compound (5-1) was used, the same results as in the example using compound (5-1) shown in Table 1 were obtained.

[0189]

[0190] 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film

Claims

1. A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1). In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent; D represents a group represented by formula (2) or a group represented by formula (3). １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (2), * represents a bonding position. Z １ and Z ２ Each of X independently represents an oxygen atom or a sulfur atom. １ and X ２ Each independently represents -NR Ｎ１ represents an oxygen atom, a sulfur atom, or a selenium atom. Ｎ１ represents a hydrogen atom or a substituent. １ and Ar ２ Each of the symbols independently represents an aromatic ring which may have a substituent. In formula (3), * represents a bonding position. Z ３ and Z ４ Each of X independently represents an oxygen atom or a sulfur atom. ３ and X ４ Each independently represents -NR Ｎ２ represents an oxygen atom, a sulfur atom, or a selenium atom. Ｎ２ represents a hydrogen atom or a substituent. ３ and Ar ４ Each of the symbols independently represents an aromatic ring which may have a substituent. In formula (A-1), * represents a bonding position. １ represents a ring containing two or more carbon atoms and which may have a substituent. １ is an oxygen atom, a sulfur atom, ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. In formula (A-2), * represents a bonding position. R ｂ１ and R ｂ２ each independently represents a cyano group, -COOR ｂ３ , -COR ｂ４ , -SOR ｂ５ , or -SO ２ R ｂ６ Represents: R ｂ３ ~R ｂ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

2. The photoelectric conversion element according to claim 1, wherein the group represented by formula (2) is a group represented by formula (2-1) or a group represented by formula (2-2), and the group represented by formula (3) is a group represented by formula (3-1) or a group represented by formula (3-2). In formula (2-1), Y １ ~Y ４ One of them represents -C(*)=, and Y １ ~Y ４ Three of the groups are independently -CR ａ１ = or a nitrogen atom. ５ ~Y ８ One of them represents -C(*)=, and Y ５ ~Y ８ Three of the groups are independently -CR ａ１ = or a nitrogen atom. * represents the bonding position. R ａ１ Each of X independently represents a hydrogen atom or a substituent. １ , X ２ , Z １ , and Z ２ are X in the formula (2), １ , X ２ , Z １ , and Z ２ In formula (2-2), * represents a bonding position. X ５ and X ６ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ３ -, and the other is -CR ａ２ = or a nitrogen atom. X ７ and X ８ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ３ -, and the other is -CR ａ２ = or a nitrogen atom. ａ２ and R Ｎ３ Each of X independently represents a hydrogen atom or a substituent. １ , X ２ , Z １ , and Z ２ are X in the formula (2), １ , X ２ , Z １ , and Z ２ In formula (3-1), Y ９ ~Y １２ One of them represents -C(*)=, and Y ９ ~Y １２ Three of the groups are independently -CR ａ３ = or a nitrogen atom. １３ ~Y １６ One of them represents -C(*)=, and Y １３ ~Y １６ Three of the groups are independently -CR ａ３ = or a nitrogen atom. * represents the bonding position. R ａ３ Each of X independently represents a hydrogen atom or a substituent. ３ , X ４ , Z ３ , and Z ４ respectively represent X in the formula (3). ３ , X ４ , Z ３ , and Z ４ In formula (3-2), * represents a bonding position. X ９ and X １０ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ４ -, and the other is -CR ａ４ = or a nitrogen atom. X １１ and X １２ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ４ -, and the other is -CR ａ４ = or a nitrogen atom. ａ４ and R Ｎ４ Each of X independently represents a hydrogen atom or a substituent. ３ , X ４ , Z ３ , and Z ４ respectively represent X in the formula (3). ３ , X ４ , Z ３ , and Z ４ is the same as:

3. The photoelectric conversion element according to claim 1, wherein the group represented by formula (A-1) is a group represented by formula (A-3). In formula (A-3), * represents a bonding position. ２ represents a ring containing 3 or more carbon atoms and which may have a substituent. ２ and W ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

4. A １ and A ２ are each independently a group represented by formula (C-1) or formula (C-2). In formula (C-1), * represents a bonding position. ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. ３ represents an aromatic ring which may have a substituent. In formula (C-2), * represents a bonding position. X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ R each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent.

5. In the formula (2), X １ and X ２ But -NR Ｎ１ - and R Ｎ１ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted aromatic ring group, ３ and X ４ But -NR Ｎ２ - and R Ｎ２ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or an aromatic ring group which may have a substituent.

6. R Ｎ１ represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T; Ｎ２ represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from Substituent Group T. Substituent Group T: A linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and -Si(R Ｓｉ４ ) ３ A group represented by the formula: Ｓｉ４ each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned substituent group T, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group T.

7. The photoelectric conversion element according to any one of claims 1 to 4, wherein the photoelectric conversion film further contains an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed in a state in which the compound represented by formula (1) and the n-type organic semiconductor are mixed.

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

9. The photoelectric conversion element according to any one of claims 1 to 4, wherein the photoelectric conversion film further contains a p-type organic semiconductor.

10. The photoelectric conversion element according to any one of claims 1 to 4, wherein the photoelectric conversion film further contains a dye.

11. The photoelectric conversion element according to any one of claims 1 to 4, further comprising one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

12. An imaging device comprising the photoelectric conversion element according to any one of claims 1 to 4.

13. An optical sensor comprising the photoelectric conversion element according to any one of claims 1 to 4.

14. A method for manufacturing an imaging element, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 4.

15. A compound represented by formula (1). In formula (1), R １ and R ２ each independently represents a hydrogen atom or a substituent; D represents a group represented by formula (2) or a group represented by formula (3). １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (2), * represents a bonding position. Z １ and Z ２ Each of X independently represents an oxygen atom or a sulfur atom. １ and X ２ Each independently represents -NR Ｎ１ represents an oxygen atom, a sulfur atom, or a selenium atom. Ｎ１ represents a hydrogen atom or a substituent. １ and Ar ２ Each of the symbols independently represents an aromatic ring which may have a substituent. In formula (3), * represents a bonding position. Z ３ and Z ４ Each of X independently represents an oxygen atom or a sulfur atom. ３ and X ４ Each independently represents -NR Ｎ２ represents an oxygen atom, a sulfur atom, or a selenium atom. Ｎ２ represents a hydrogen atom or a substituent. ３ and Ar ４ Each of the symbols independently represents an aromatic ring which may have a substituent. In formula (A-1), * represents a bonding position. １ represents a ring containing two or more carbon atoms and which may have a substituent. １ is an oxygen atom, a sulfur atom, ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. In formula (A-2), * represents a bonding position. R ｂ１ and R ｂ２ each independently represents a cyano group, -COOR ｂ３ , -COR ｂ４ , -SOR ｂ５ , or -SO ２ R ｂ６ Represents: R ｂ３ ~R ｂ６ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

16. The compound according to claim 15, wherein the group represented by formula (2) is a group represented by formula (2-1) or a group represented by formula (2-2), and the group represented by formula (3) is a group represented by formula (3-1) or a group represented by formula (3-2). In formula (2-1), Y １ ~Y ４ One of them represents -C(*)=, and Y １ ~Y ４ Three of the groups are independently -CR ａ１ = or a nitrogen atom. ５ ~Y ８ One of them represents -C(*)=, and Y ５ ~Y ８ Three of the groups are independently -CR ａ１ = or a nitrogen atom. * represents the bonding position. R ａ１ Each of X independently represents a hydrogen atom or a substituent. １ , X ２ , Z １ , and Z ２ are X in the formula (2), １ , X ２ , Z １ , and Z ２ In formula (2-2), * represents a bonding position. X ５ and X ６ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ３ -, and the other is -CR ａ２ = or a nitrogen atom. X ７ and X ８ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ３ -, and the other is -CR ａ２ = or a nitrogen atom. ａ２ and R Ｎ３ Each of X independently represents a hydrogen atom or a substituent. １ , X ２ , Z １ , and Z ２ are X in the formula (2), １ , X ２ , Z １ , and Z ２ In formula (3-1), Y ９ ~Y １２ One of them represents -C(*)=, and Y ９ ~Y １２ Three of the groups are independently -CR ａ３ = or a nitrogen atom. １３ ~Y １６ One of them represents -C(*)=, and Y １３ ~Y １６ Three of the groups are independently -CR ａ３ = or a nitrogen atom. * represents the bonding position. R ａ３ Each of X independently represents a hydrogen atom or a substituent. ３ , X ４ , Z ３ , and Z ４ respectively represent X in the formula (3). ３ , X ４ , Z ３ , and Z ４ In formula (3-2), * represents a bonding position. X ９ and X １０ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ４ -, and the other is -CR ａ４ = or a nitrogen atom. X １１ and X １２ one of the groups is a sulfur atom, an oxygen atom, a selenium atom, or -NR Ｎ４ -, and the other is -CR ａ４ = or a nitrogen atom. ａ４ and R Ｎ４ Each of X independently represents a hydrogen atom or a substituent. ３ , X ４ , Z ３ , and Z ４ respectively represent X in the formula (3). ３ , X ４ , Z ３ , and Z ４ is the same as:

17. The compound according to claim 15, wherein the group represented by formula (A-1) is a group represented by formula (A-3). In formula (A-3), * represents a bonding position. ２ represents a ring containing 3 or more carbon atoms and which may have a substituent. ２ and W ３ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.

18. A １ and A ２ are each independently a group represented by formula (C-1) or formula (C-2). In formula (C-1), * represents a bonding position. ｃ１ and X ｃ２ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. ３ represents an aromatic ring which may have a substituent. In formula (C-2), * represents a bonding position. X ｃ３ ~X ｃ５ each independently represents an oxygen atom, a sulfur atom, or ═NR Ｗ２ , or = CR Ｗ３ R Ｗ４ Represents R Ｗ２ represents a hydrogen atom or a substituent. Ｗ３ and R Ｗ４ each independently represents a cyano group, —SO ２ R Ｗ５ , -COOR Ｗ６ , or -COR Ｗ７ Represents Ｗ５ ~R Ｗ７ R each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent.

19. In the formula (2), X １ and X ２ But -NR Ｎ１ - and R Ｎ１ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted aromatic ring group, ３ and X ４ But -NR Ｎ２ - and R Ｎ２ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aliphatic heterocyclic group, or an optionally substituted aromatic ring group.

20. R Ｎ１ represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group T; Ｎ２ represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group which may have a substituent selected from Substituent Group T. Substituent Group T: A linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and -Si(R Ｓｉ４ ) ３ A group represented by the formula: Ｓｉ４ each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned substituent group T, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group T.

Images