Photoelectric conversion element, imaging element, method for manufacturing imaging element, light sensor, compound

Abstract

To provide: a photoelectric conversion element with excellent response speed upon receiving red light, and small field strength dependence of the response speed; and an imaging element, a method for manufacturing the imaging element, a light sensor and a compound that are related to the photoelectric conversion element.SOLUTION: A photoelectric conversion element comprises a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, where the photoelectric conversion film contains a compound represented by the formula (1).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art In recent years, the development of elements having photoelectric conversion films and organic electroluminescence (EL) elements as organic electronic devices has progressed. For example, Patent Document 1 discloses an organic EL device using a silacyclopentadiene derivative having a specific structure. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2005-310441 A Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, with the demand for improved performance of imaging elements and optical sensors, there is a demand for photoelectric conversion elements that exhibit excellent characteristics. For example, the characteristics required for the photoelectric conversion element include an excellent response speed when receiving red light. In addition, it is also required that the response speed of the photoelectric conversion element does not decrease easily even when the electric field strength is changed, that is, the response speed has a small electric field strength dependency. In response to such demands, the present inventors have produced and investigated a photoelectric conversion element using the compound disclosed in Patent Document 1, and have found that there is a need for improvement in terms of achieving both excellent response speed and small electric field intensity dependency of the response speed when red light is received. Note that the above-mentioned red light means light having 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 red light is received and has a small dependency of the response speed on the electric field strength. Another object of the present invention is to provide an imaging element, a manufacturing method for an imaging element, an optical sensor, and a compound related to the above-mentioned photoelectric conversion element. [Means for solving the problem]

[0006] As a result of intensive 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, The photoelectric conversion element, wherein the photoelectric conversion film contains a compound represented by formula (1) described below. [2] The photoelectric conversion element according to [1], wherein the compound represented by the formula (1) is a compound represented by any one of the formulas (2) to (4) described below. [3] R c1 and R c2 At least one of the groups represents a group selected from the substituent group S described below, R c3 and R c4 At least one of the above represents a group selected from the above substituent group S, R c5 and R c6 At least one of the following represents a group selected from the above-mentioned Substituent Group S: [4] X 1 -C(R c1 R c2 )-, R c1 and R c2 each independently represents a group selected from the above-mentioned substituent group S; X 1 -Si(R c3 R c4 )-, R c3 and R c4 each independently represents a group selected from the above-mentioned substituent group S. [5] X 1 -C(R c1 R c2 )-, R c1and R c2 each independently represents a group selected from the substituent group P described below, X 1 -Si(R c3 R c4 )-, R c3 and R c4 each independently represents a group selected from the above-mentioned substituent group P. [6] Y 1 and Y 2 each independently represents an aromatic ring which may have a halogen atom. [7] The photoelectric conversion element according to any one of [1] to [6], wherein the group represented by formula (A-1) described later is a group represented by formula (A-3) described later. [8] A 1 and A 2 are each independently a group represented by formula (C-1) or formula (C-2) described later. [9] The photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion element according to any one of [1] to [8], wherein the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) described below with the n-type organic semiconductor.

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

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

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

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

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

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

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

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

[13] .

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

[13] .

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

[13] .

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

[18] The compound according to

[17] , wherein the compound represented by the formula (1) is a compound represented by any one of the formulas (2) to (4) described below.

[19] R c1 and R c2 At least one of the groups represents a group selected from the substituent group S described below, R c3 and R c4 At least one of the above represents a group selected from the above substituent group S, R c5 and R c6 At least one of the following represents a group selected from the above-mentioned substituent group S:

[20] X 1 -C(R c1 R c2 )-, and R c1 and R c2 each independently represents a group selected from the above-mentioned substituent group S; X 1 -Si(R c3 R c4 )-, and R c3 and R c4 each independently represents a group selected from the above-mentioned substituent group S.

[21] X 1 -C(R c1 R c2 )-, and R c1 and R c2 each independently represents a group selected from the substituent group P described below, X 1 -Si(R c3 R c4 )-, and R c3 and R c4each independently represents a group selected from the above-mentioned substituent group P.

[22] Y 1 and Y 2 each independently represents an aromatic ring which may have a halogen atom.

[23] The compound according to any one of

[17] to

[22] , wherein the group represented by formula (A-1) described later is a group represented by formula (A-3) described later.

[24] A 1 and A 2 are each independently a group represented by formula (C-1) or formula (C-2) described later. Effect of the Invention

[0008] According to the present invention, it is possible to provide a photoelectric conversion element which has an excellent response speed when red light is received and in which the response speed has a small dependency on the electric field strength. Furthermore, according to the present invention, there can be provided an imaging element, a manufacturing method for an imaging element, an optical sensor, and a compound related to the above-mentioned photoelectric conversion element. [Brief description of the drawings]

[0009] [Figure 1] FIG. 2 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element. [Diagram 2] FIG. 2 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0011] The following describes the meaning of each description in this specification. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, a hydrogen atom may be a protium atom (a normal hydrogen atom) or a deuterium atom (eg, a deuterium atom, etc.).

[0012] In this specification, for a compound that may have geometric isomers (cis-trans isomers), the general formula or structural formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such a case, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.

[0013] The bond direction of a divalent group (e.g., -CO-O-, etc.) described in this specification is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "XYZ", the compound may be either "XO-CO-Z" or "X-CO-OZ".

[0014] The symbol "*" in a chemical formula indicates a bond position unless otherwise specified. In this specification, when there are a plurality of substituents and linking groups, etc., represented by specific symbols (hereinafter also referred to as "substituents, etc."), or when a plurality of substituents, etc., are simultaneously specified, it means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc. In this specification, unless otherwise specified, examples of the "substituent" include the groups exemplified as the substituent W described later.

[0015] (substituent W) The substituent W in this specification will be described. The substituent W can be, for example, a halogen atom (e.g., 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 alkyl group include an alkyloxy group, a primary, secondary or tertiary amino group (including 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. In addition, each of the above groups may further have a substituent (for example, one or more of the above groups) if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. When the substituent W has a carbon atom, the substituent W has 1 to 20 carbon atoms, for example. The number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30. In addition, it is also preferable that the specific compound described later does not have a carboxy group, a salt of a carboxy group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH)2) and / or a primary amino group as a substituent.

[0016] In this specification, the aliphatic hydrocarbon group may be any of linear, branched, and cyclic. Furthermore, the phrase "the aliphatic hydrocarbon group may have an etheric oxygen atom" means that the aliphatic hydrocarbon group may have a divalent linking group represented by -O- in the middle or at the end. 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 alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and a cyclopentyl group. The alkyl group may be any one of a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, and may have these ring structures as partial structures. In the alkyl group which may have a substituent, examples of the substituent which the alkyl group may have include the groups exemplified as the substituent W. Among them, 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, and 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 which the alkoxy group may have include the same substituents as those in the alkyl group which may have a substituent. In the alkylthio group which may have a substituent, examples of the substituent which the alkylthio group may have include the same substituents as those in the alkyl group which may have a substituent.

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

[0019] In this specification, an aromatic ring or an aromatic ring constituting an aromatic ring group may be either a monocyclic ring or a polycyclic ring (e.g., 2 to 6 rings, etc.) unless otherwise specified. A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure. A polycyclic (e.g., 2 to 6 rings, etc.) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6, etc.) aromatic ring structures condensed as ring structures. The aromatic ring preferably has 5 to 15 ring members. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. When the aromatic ring is an aromatic heterocycle, the number of heteroatoms contained as ring member atoms is, for example, 1 to 10. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom and a boron atom. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, 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), and an imidazooxazole ring (e.g., an imidazo[2,1-b]oxazole ring). , thienothiazole ring (e.g., thieno[2,3-d]thiazole ring, etc.), benzothiadiazole ring, benzodithiophene ring (e.g., benzo[1,2-b:4,5-b']dithiophene ring, etc.), thienothiophene ring (e.g., thieno[3,2-b]thiophene ring, etc.), thiazolothiazole ring (e.g., thiazolo[5,4-d]thiazole ring, etc.), naphthodithiophene ring (e.g., naphtho[2,3 -b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc.), benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring, and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring.

[0020] In this specification, the term "aromatic ring group" includes, for example, a group obtained by removing one or more (for example, 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic ring. In this specification, the term aryl group includes, for example, a group obtained by removing one hydrogen atom from a ring that corresponds to an aromatic hydrocarbon ring among the above aromatic rings. In this specification, the term "heteroaryl group" includes, for example, a group in which one hydrogen atom has been removed from a ring corresponding to an aromatic heterocycle among the above aromatic rings. In this specification, the term "arylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring that corresponds to an aromatic hydrocarbon ring among the above aromatic rings. In this specification, the term "heteroarylene group" includes, for example, a group formed by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above aromatic rings. In the aromatic ring which may have a substituent, the aromatic ring group which may have a substituent, the aryl group which may have a substituent, the heteroaryl group which may have a substituent, the arylene group which may have a substituent, and the heteroarylene group which may have a substituent, the types of the substituents which these may have include, for example, the groups exemplified as the substituent W. When these groups which may have a substituent have a substituent, the number of the substituents may be 1 or more (for example, 1 to 4, etc.).

[0021] In this specification, the term "non-aromatic ring" refers to a ring structure that is not aromatic, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle. Examples of the aliphatic hydrocarbon ring include cycloalkanes, cycloalkenes, and cycloalkynes. In this specification, the term "aliphatic heterocyclic group" includes, for example, a group obtained by removing one hydrogen atom from the above-mentioned aliphatic heterocycle. In this specification, the aliphatic heterocyclic group preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, and further preferably 6 to 8 ring members. Examples of the heteroatom contained in the aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom and a boron atom, with a sulfur atom, an oxygen atom or a nitrogen atom being preferred. Examples of the aliphatic heterocycle constituting the above-mentioned aliphatic heterocycle group include a pyrrolidine ring, an oxolane ring (tetrahydrofuran ring), a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring (pentamethylene sulfide ring), a piperazine ring, a morpholine ring, a quinuclidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, and a γ-butyrolactone ring.

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

[0023] Although the reason why the photoelectric conversion element having the above configuration can solve the problems of the present invention is not necessarily clear, the present inventors speculate as follows. The mechanism by which the effects are obtained is not limited by the following speculation. In other words, even if the effects are obtained by a mechanism other than the following, it is included in 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 have high aggregation due to their conjugated structure. The specific compound has a donor portion of a specific structure containing a specific atom as represented by formula (1), thereby suppressing excessive aggregation between the specific compounds in the photoelectric conversion film, and efficient charge separation can be achieved. As a result, a photoelectric conversion element containing the specific compound is considered to have an excellent response speed and a small electric field strength dependency of the response speed. Hereinafter, achieving at least one of a better response speed and a smaller dependency of the response speed on the electric field strength is also referred to as "the effect of the present invention being better."

[0024] FIG. 1 shows a schematic cross-sectional view of one embodiment of a photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 functioning as an upper electrode are stacked in this order. Fig. 2 shows a configuration example 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 laminated in this order on a lower electrode 11. The laminated order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figs. 1 and 2 may be changed as appropriate depending on the application and characteristics.

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

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

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

[0028] [ka]

[0029] In formula (1), X 1 is -C(R c1 R c2 )-, -Si(R c3 R c4 )- or -Ge(R c5 R c6 )-. R c1 , R c2 , R c3 , R c4 , R c5 and R c6 each independently represents a hydrogen atom or a substituent. R c1 and R c2 , R c3 and R c4 , and R c5 and R c6 may be bonded to each other to form a ring which may have a substituent. R Z1 and R Z2 each independently represents a hydrogen atom or a substituent. Y 1 and Y 2 each independently represents an aromatic ring which may have a substituent. R 1 and R 2 each independently represents a hydrogen atom or a substituent. A 1 and A 2 each independently represents a group represented by formula (A-1) or formula (A-2).

[0030] In formula (A-1), C 1 represents a ring containing 2 or more carbon atoms which may have a substituent. W 1 is an oxygen atom, a sulfur atom, =NR W2 or =CR W3 R W4 Represents. R W2represents a hydrogen atom or a substituent. W3 and R W4 each independently represents a cyano group, -SO2R W5 , -COOR W6 or -COR W7 Represents R 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), R b1 and R b2 each independently represents a cyano group, -COOR b3 , -COR b4 , or -SO2R b5 Represents R b3 , R b4 and R b5 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.

[0031] In formula (1), X 1 is -C(R c1 R c2 )-, -Si(R c3 R c4 )- or -Ge(R c5 R c6 )-represents. The effect of the present invention is more excellent, 1 is -C(R c1 R c2 )- or -Si(R c3 R c4 )- is preferred, and -C(R c1 R c2 )- is more preferred.

[0032] R c1 , R c2 , R c3 , R c4 , R c5 and R c6 each independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W described above. As the above-mentioned substituent, a group selected from the substituent group S is preferable, and a group selected from the substituent group P is more preferable. Substituent group S: an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and an aliphatic heterocyclic group which may have a substituent. Substituent group P: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 5 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, and phenyl groups which may have a substituent. In the substituent groups S and P, the aliphatic hydrocarbon group may have an etheric oxygen atom.

[0033] The effect of the present invention is more excellent. c1 and R c2 At least one of R preferably represents a group selected from the substituent group S (more preferably, the substituent group P), c1 and R c2 It is more preferable that both of represent a group selected from the substituent group S (more preferably, the substituent group P). The effect of the present invention is more excellent. c3 and R c4 At least one of R preferably represents a group selected from the substituent group S (more preferably, the substituent group P), c3 and R c4 It is more preferable that both of represent a group selected from the substituent group S (more preferably, the substituent group P). The effect of the present invention is more excellent. c5 and R c6 At least one of R preferably represents a group selected from the substituent group S (more preferably, the substituent group P), c5 and R c6 It is more preferable that both of represent a group selected from the substituent group S (more preferably, the substituent group P). Among them, X 1 -C(R c1 R c2 )-, and R c1 and Rc2 each independently represents a group selected from the substituent group S (more preferably, the substituent group P), or X 1 -Si(R c3 R c4 )-, R c3 and R c4 each independently represents a group selected from the substituent group S (more preferably, the substituent group P).

[0034] Examples of the aliphatic hydrocarbon group in the aliphatic hydrocarbon group which may have a substituent include a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 7 carbon atoms, and even more preferably 3 to 5 carbon atoms. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms.

[0035] The aliphatic hydrocarbon group may contain an etheric oxygen atom. Examples of the aliphatic hydrocarbon group having an etheric oxygen atom include a methoxy group, an ethoxy group, an isopropoxy group, a cyclopropoxy group, and a methoxyethyl group.

[0036] The aromatic ring group in the above aromatic ring group which may have a substituent may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group. The aromatic ring group may be either a monocyclic or polycyclic group. The aromatic ring group preferably has 5 to 15 ring members, more preferably 5 to 10 ring members, and further preferably 5 to 6 ring members. The aromatic ring group which may have a substituent preferably has 1-30 carbon atoms (the number of carbon atoms including the carbon atoms in the substituent), more preferably 3-20 carbon atoms, and even more preferably 4-10 carbon atoms. Examples of the heteroatom 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, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferable. Specific examples of the aromatic ring group are as described above, and are preferably a phenyl group, a thiophene ring group, a furan ring group, a thiazole ring group, an oxazole ring group, or a pyridine ring group, more preferably a phenyl group or a thiophene ring group, and even more preferably a phenyl group. 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.

[0037] The aliphatic heterocyclic group in the above-mentioned optionally substituted aliphatic heterocyclic group may be either a monocyclic group or a polycyclic group. The aliphatic heterocyclic group preferably has 3 to 20 ring members, more preferably 3 to 10 ring members, and further preferably 3 to 6 ring members. The aliphatic heterocyclic group which may have a substituent preferably has 1-30 carbon atoms (the number of carbon atoms including the carbon atoms in the substituent), more preferably 3-20 carbon atoms, and further preferably 4-10 carbon atoms. Examples of the heteroatom contained in the aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom and a boron atom, with a sulfur atom, an oxygen atom or a nitrogen atom being preferred. Specific examples of the aliphatic heterocyclic group are as described above, and a thiolane ring group, a piperidine ring group, a tetrahydrofuran ring group, or a tetrahydropyran ring group is preferred. When the aliphatic heterocyclic group has a substituent, the number of the substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.

[0038] Examples of the substituent that the aliphatic hydrocarbon group, aromatic ring group, and aliphatic heterocyclic group may have include the substituents exemplified for the substituent W described above, and a substituent selected from the substituent group T is preferred. Substituent group T: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms, aromatic ring groups which may have a substituent, silyl groups, and halogen atoms. The linear, branched and cyclic aliphatic hydrocarbon groups in the substituent group T may have an etheric oxygen atom or may be halogenated.

[0039] The silyl group is, for example, -Si(R Si ) 3. Si each independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent. R Si The definitions and preferred embodiments of the aliphatic hydrocarbon group and aromatic ring group represented by the following formula are the same as those of the aliphatic hydrocarbon group and aromatic ring group in the above-mentioned substituent group S. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.

[0040] R c1 and R c2 , R c3 and R c4 , and R c5 and R c6 may be bonded to each other to form a ring which may have a substituent. The ring may be either an aromatic ring or a non-aromatic ring, and may be either a monocyclic ring or a polycyclic ring. The ring may have a heteroatom, such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, and is preferably a sulfur atom, a nitrogen atom, or an oxygen atom. The ring preferably has 3 to 20 ring members, and more preferably 5 to 12 ring members. Examples of the substituent that the ring may have include the substituents exemplified for the substituent W above, and a substituent selected from the substituent group T above is preferred.

[0041] In formula (1), R Z1 and R Z2 each independently represents a hydrogen atom or a substituent. R Z1 and R Z2 Examples of the substituent represented by the formula (I) include the substituents exemplified for the substituent W described above, and a group selected from the above-mentioned substituent group S is preferable, and a group selected from the above-mentioned substituent group P is more preferable. X 1 -Si(R c3 R c4 )-, R in formula (1) Z1 and R Z2 each independently represents a group selected from the substituent group S.

[0042] In formula (1), Y 1 and Y 2 each independently represents an aromatic ring which may have a substituent. The "aromatic ring" in this specification is as defined above, and may be either a monocyclic ring or a polycyclic ring, and may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of ring members in the aromatic ring is not particularly limited, but is preferably 5 to 15, and more preferably 5 to 10. Y 1 and Y 2 As the ring atom, an aromatic heterocycle is preferable, and an aromatic heterocycle having at least one of an oxygen atom and a sulfur atom as a ring member atom is more preferable.

[0043] Examples of the aromatic hydrocarbon ring include the rings exemplified above. The number of heteroatoms contained as ring member atoms in the aromatic heterocycle is preferably 1 to 5, and more preferably 1 or 2. 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 heterocycle include the rings exemplified above.

[0044] Y 1 and Y 2 Examples of the substituent that the aromatic ring represented by the formula (I) may have include the substituents exemplified for the substituent W described above, and a group selected from the above substituent group S (an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group), a halogen atom, a cyano group, a silyl group, or an optionally substituted acyl group.

[0045] The halogen atom is preferably a chlorine atom or a fluorine atom. The silyl group includes the above-mentioned -Si(R Si ) 3.

[0046] The hydrocarbon group contained in the acyl group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. The definitions and preferred embodiments of the aliphatic hydrocarbon group and aromatic hydrocarbon group contained in the acyl group are the same as those of the aliphatic hydrocarbon group and aromatic hydrocarbon group in the substituent group S above. The acyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, and a benzoyl group, and an acetyl group or a propionyl group is preferable. Examples of the substituent that the acyl group may have include the substituents exemplified as the substituent W described above, and a substituent selected from the substituent group T is preferred.

[0047] Y 1 and Y 2 are preferably each independently an aromatic ring which may have a halogen atom.

[0048] In terms of better effects of the present invention, the compound represented by the above formula (1) is preferably a compound represented by any one of formulas (2) to (4).

[0049] [ka]

[0050] In formulas (2) to (4), X 2 and X 3 each independently represents an oxygen atom, a sulfur atom, or -NR 3 - or a selenium atom. Z 1 ~Z 12 are each independently, =CR 4 - or a nitrogen atom. R 3 and R 4 each independently represents a hydrogen atom or a substituent. X 1 , R Z1 , R Z2 , R 1 , R 2 , A 1 and A 2 is X in the above formula (1). 1 , R Z1 , R Z2 , R 1 , R 2 , A 1 and A 2 Also, X 1 , R Z1 , R Z2 , R 1 , R 2 , A 1 and A 2 In the preferred embodiment, X in formula (1) 1 , R Z1 , R Z2 , R 1 , R 2 , A 1 and A 2 Same as R 1 , R 2 , A 1 and A 2 This will be described in more detail later.

[0051] In formulas (2) to (4), X 2 and X 3 each independently represents an oxygen atom, a sulfur atom, or -NR 3 - or a selenium atom. R 3 each independently represents a hydrogen atom or a substituent. R 3 Examples of the substituent represented by the formula (I) include the groups exemplified as the substituent W described above, and among them, a group selected from the above-mentioned substituent group S is preferable, and a group selected from the above-mentioned substituent group P is more preferable. X 2 and X 3 At least one of the groups is preferably an oxygen atom or a sulfur atom, and more preferably both of the groups are oxygen atoms or sulfur atoms.

[0052] In formulas (2) to (4), Z 1 ~Z 12 are each independently, =CR 4 - or a nitrogen atom. R 4 each independently represents a hydrogen atom or a substituent. R 4 Examples of the substituent represented by the formula (I) include the groups exemplified as the substituent W described above, and among these, a group selected from the above-mentioned substituent group S (an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group), a halogen atom, a cyano group, a silyl group, or an optionally substituted acyl group. The definitions and preferred embodiments of the silyl group and the acyl group which may have a substituent are described in Y 1 Or Y 2 The substituent that the aromatic ring represented by the formula (I) may have is as described in detail above. R 4 It is preferable that each independently represents a hydrogen atom or a halogen atom.

[0053] In formula (2), Z 1 ~Z 4 Both are =CR4 - is preferred. In formula (3), Z 1 , Z 2 , and Z 5 ~Z 8 Both are =CR 4 - is preferred. In formula (4), Z 5 ~Z 12 Both are =CR 4 - is preferred.

[0054] In formulas (1) to (4), 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 described above. The effect of the present invention is more excellent. 1 and R 2 is preferably a hydrogen atom.

[0055] In formulas (1) to (4), A 1 and A 2 each independently represents a group represented by formula (A-1) or formula (A-2). The group represented by formula (A-1) or formula (A-2) will be described in detail below.

[0056] [ka]

[0057] In formula (A-1), C 1 represents a ring containing two or more carbon atoms and 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 clearly shown in the formula. The ring may be either an aromatic ring or a non-aromatic ring. The ring may be either a monocycle or a polycycle, 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 further preferably 8 to 10.

[0058] The ring may have a heteroatom, such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, and is preferably a sulfur atom, a nitrogen atom, or an oxygen atom. The number of heteroatoms in the ring is preferably 0 to 10, and more preferably 0 to 5. Above C 1 Among the carbon atoms constituting the ring represented by the formula (A-1), the carbon atom at the bonding position marked with * and W 1 Carbon atoms other than the carbon atom bonded to the may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0059] Above C 1 The ring represented by the formula (I) is preferably a ring used as an acidic nucleus (for example, an acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, 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, 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one, and the like. (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, etc. (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 its derivatives, etc. 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, etc. (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, etc. (i) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc. (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, and the like. (o) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione. (p) Benzothiophen-3(2H)-one nucleus: for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, dioxobenzothiophen-3(2H)-one, and the like. (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. (r) Benzofuran-3-(2H)-one nucleus: for example, benzofuran-3-(2H)-one, etc. (s) 2,2-dihydrophenalene-1,3-dione nucleus, etc.

[0060] In formula (A-1), W 1 is an oxygen atom, a sulfur atom, =NR W2 or =CR W3 R W4 Represents. W 1 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom, in terms of obtaining better effects of the present invention. R W2 represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W above. R W3 and R W4 each independently represents a cyano group, -SO2R W5 , -COOR W6 or -COR W7 Represents. R W5 ~R W7each 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. The aliphatic hydrocarbon group is as defined above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The aromatic ring group is as defined above, and is preferably an aromatic hydrocarbon group, more preferably a phenyl group. The aliphatic heterocyclic group is as defined above, and the heteroatom contained in the aliphatic heterocyclic group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. R W5 ~R W7 Examples of the substituent that may be possessed by each group represented by the following formula (I) include the substituents exemplified for the substituent W above.

[0061] In formula (A-2), R b1 and R b2 each independently represents a cyano group, -COOR b3 , -COR b4 , or -SO2R b5 represents a cyano group or -COR b4 is preferred. R b3 , R b4 and R b5 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. R b3 , R b4 and R b5 The definitions and preferred embodiments of each group represented by R W5 ~R W7 Among them, an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a phenyl group is preferred.

[0062] The group represented by the above formula (A-1) is preferably a group represented by the formula (A-3) in that the effects of the present invention are more excellent.

[0063] [ka]

[0064] In formula (A-3), C 2 represents a ring containing 3 or more carbon atoms which may have a substituent. Above C 2 The three carbon atoms contained in are the three carbon atoms specified in formula (A-3). The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the ring is the number including the three carbon atoms clearly shown in the formula. The ring may be either an aromatic ring or a non-aromatic ring. The ring may be either a monocycle or a polycycle, 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 further preferably 8 to 10. The ring may have a heteroatom, such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, and is preferably a sulfur atom, a nitrogen atom, or an oxygen atom. The number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5. Above C 2 Among the carbon atoms constituting the ring represented by the formula (A-3), the carbon atom at the bonding position marked with * and W 2 Or W 3 Carbon atoms other than the carbon atom bonded to the may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S). C 2 The ring represented by the formula: is preferably the ring used as the acidic nucleus. Preferred embodiments of the substituent that the above ring may have include the above-mentioned ring C 1 The substituents are the same as those that may be possessed by the group.

[0065] In formula (A-3), W 2 and W 3 is an oxygen atom, a sulfur atom, =NRW2 or =CR W3 R W4 The effect of the invention is more excellent. 2 and W 3 is preferably an oxygen atom. R W2 , R W3 and R W4 is R in formula (A-1) W2 , R W3 and R W4 The same applies to preferred embodiments.

[0066] The effect of the present invention is more excellent. 1 and A 2 is more preferably a group represented by formula (C-1) or formula (C-2).

[0067] [ka]

[0068] In formula (C-1), X c1 and X c2 are each independently an oxygen atom, a sulfur atom, or =NR W2 or =CR W3 R W4 The effect of the present invention is more excellent, c1 and X c2 At least one of X is preferably an oxygen atom. c1 and X c2 It is more preferable that is an oxygen atom. R W2 , R W3 and R W4 is R in formula (A-1) W2 , R W3 and R W4 The same applies to preferred embodiments.

[0069] In formula (C-1), C 3 represents an aromatic ring which may have a substituent. The aromatic ring may be either a monocyclic ring or a polycyclic ring. The number of ring members in the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and further 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 heterocycle, with an aromatic hydrocarbon ring being preferred. Above C 3 The 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, a thienothiophene 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 for the substituent W above, 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.

[0070] In formula (C-2), X c3 ~X c5 are each independently an oxygen atom, a sulfur atom, or =NR W2 or =CR W3 R W4 The effect of the present invention is more excellent, c3 and X c4 is preferably an oxygen atom, and X c3 ~X c5 It is more preferable that is an oxygen atom. R W2 , R W3 and R W4 is R in formula (A-1) W2 , R W3 and R W4 The same applies to preferred embodiments.

[0071] In formula (C-2), R c1 and R c2 each independently represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified as the substituent W above, and an alkyl group or an aryl group is preferable, and an alkyl group is more preferable. The alkyl group may be linear, branched, or cyclic, and is preferably linear. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The aryl group may be either a monocyclic or polycyclic ring, and is preferably a phenyl group. The aryl group may further have a substituent, and examples of the substituent include the groups exemplified by the substituent W.

[0072] A 1 and A 2 is preferably a group represented by formula (A-1), more preferably a group represented by formula (A-3), further preferably a group represented by formula (C-1) or a group represented by formula (C-2), particularly preferably a group represented by formula (C-2). Also, A 1 and A 2 may be the same or different, but are preferably the same.

[0073] Specific examples of the specific compound are shown below, but the present invention is not limited to these.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] In the specific compounds exemplified above, A represents any one of the following groups.

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] The molecular weight of the specific compound is preferably 300-1,000, more preferably 400-900, and even more preferably 400-800. When the molecular weight is within the above range, it is presumed that the sublimation temperature of the specific compound is low, resulting in excellent suitability for production.

[0086] 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, the specific compound preferably has an ionization potential of −5.0 to −6.0 eV in a single film.

[0087] The maximum absorption wavelength of the specific compound is preferably in the range of 550 to 800 nm, and more preferably in the range of 600 to 780 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of a specific compound to a concentration such that the absorbance is between 0.5 and 1.0. However, if the specific compound is insoluble in chloroform, the value measured using the specific compound in a film state formed by vapor deposition of the specific compound is taken as the maximum absorption wavelength of the specific compound.

[0088] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, a photosensor, or a photovoltaic cell. The specific compound often functions as a dye in the photoelectric conversion film. Further, the specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic agent material.

[0089] The specific compound may be purified as needed. Examples of the purification method of the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, slurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.

[0090] The content of the specific compound in the photoelectric conversion film (= film thickness in terms of a single layer of the specific compound / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and still more preferably 20 to 50% by volume. Only one kind of the specific compound may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

[0091] <n-type organic semiconductor> The photoelectric conversion film preferably further contains an n-type organic semiconductor in addition to the above specific compound. The n-type organic semiconductor is a compound different from the above specific compound. An n-type organic semiconductor is an acceptor organic semiconductor material (compound), which is an organic compound that has the property of easily accepting electrons. In other words, an n-type organic semiconductor is the organic compound that has the greater electron affinity when two organic compounds are used in contact with each other. In other words, any organic compound that has electron-accepting properties can be used as an acceptor organic semiconductor. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerene and its derivatives; condensed aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); and 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole). polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 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 JP2006-100767A.

[0092] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerene and derivatives thereof are preferred. As a fullerene, for example, fullerene C 60 , Fullerene C 70 , Fullerene C 76 , Fullerene C 78 , Fullerene C80 , Fullerene C 82 , Fullerene C 84 , Fullerene C 90 , Fullerene C 96 , Fullerene C 240 , Fullerene C 540 and mixed fullerenes. The fullerene derivative may be, for example, a compound in which a substituent is added to the fullerene. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. The fullerene derivative is preferably a compound described in JP-A-2007-123707.

[0093] The n-type organic semiconductor may be an organic dye. Examples of organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0094] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.

[0095] 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.

[0096] The photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in which a specific compound and an n-type organic semiconductor are mixed and dispersed in the photoelectric conversion film. The photoelectric conversion film having the 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.

[0097] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0098] The n-type organic semiconductors may be used alone or in combination of two or more. When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (film thickness of n-type organic semiconductor in terms of a single layer / film thickness of photoelectric conversion film × 100) is preferably 15 to 75 volume %, more preferably 20 to 60 volume %, and even more preferably 20 to 50 volume %.

[0099] 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. The fullerenes may be used alone or in combination of two or more kinds.

[0100] 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 of the specific compound in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the n-type organic semiconductor in terms of a single layer)×100) is preferably 20 to 80% by volume, and more preferably 40 to 80% by volume. 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 of the specific compound in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the n-type organic semiconductor in terms of a single layer+film thickness of the p-type organic semiconductor in terms of a single layer)×100) is preferably 15 to 75 vol%, more preferably 30 to 75 vol%. In addition, the photoelectric conversion film is preferably substantially composed of a specific compound, an n-type organic semiconductor, and a p-type organic semiconductor optionally contained. "Substantially" means that the total content of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume with respect to the total mass of the photoelectric conversion film.

[0101] <p-type organic semiconductor> The photoelectric conversion film preferably further contains a p-type organic semiconductor in addition to the above specific compound. The p-type organic semiconductor is a compound different from the above specific compound. The p-type organic semiconductor is a donor-type organic semiconductor material (compound), which refers to an organic compound having a property of easily donating electrons. That is, the p-type organic semiconductor refers to the organic compound with a smaller ionization potential when two organic compounds are brought into contact and used. The p-type organic semiconductor may be used alone or in combination of two or more.

[0102] 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), the compounds described in paragraphs

[0128] to

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

[0052] to

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

[0119] to

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

[0044] to

[0051] of JP 2015-153910 A and compounds described in paragraphs

[0086] to

[0090] of JP 2012-094660 A, etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (e.g., thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzthiophene (BTBT) derivatives, thiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

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

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

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

[0015] to

[0025] of WO2018 / 207722A, and compounds described in paragraphs

[004] to

[0025] of JP2019-054228A. 5] to

[0053] , compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

[0036] of JP2019-080052A, compounds described in paragraphs

[0044] to

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

[0041] to

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

[0034] to

[0037] of JP2019-050398A,Compounds described in paragraphs

[0033] to

[0036] of JP 2018-206878 A, compounds described in paragraph

[0038] of JP 2018-190755 A, compounds described in paragraphs

[0019] to

[0021] of JP 2018-026559 A, compounds described in paragraphs

[0031] to

[0056] of JP 2018-170487 A, compounds described in paragraphs

[0036] to

[0041] of JP 2018-078270 A, compounds described in paragraphs

[0036] to

[0041] of JP 2018-16620 A Compounds described in paragraphs

[0055] to

[0082] of JP 2018-113425 A, compounds described in paragraphs

[0041] to

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

[0044] to

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

[0041] to

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

[0042] to

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

[0042] to

[0049] of JP 2018-014474 A Compounds described in paragraphs

[0031] to

[0036] of WO2018 / 016465, compounds described in paragraphs

[0036] to

[0046] of JP2020-016465A, compounds described in paragraphs

[0045] to

[0048] of JP2020-010024A, etc.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbon ring compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. As p-type organic semiconductors, in addition to the compounds described above, compounds described in JP 2021-163968 A, JP 2022-027575 A, JP 2022-123944 A, JP 2022-122839 A, JP 2022-120323 A, JP 2022-120273 A, JP 2022-115832 A, JP 2022-108268 A, JP 2022-100258 A, JP 2022-181226 A, and JP 2023-005703 A can also be used, and these compounds are incorporated herein. Examples of p-type organic semiconductors include compounds having a smaller ionization potential than n-type organic semiconductors. If this condition is satisfied, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as the p-type organic semiconductor compound are given below.

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0108] The p-type organic semiconductor material may be used alone or in combination of two or more. When the photoelectric conversion film contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the photoelectric conversion film (film thickness of the p-type organic semiconductor in terms of a single layer / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75 volume %, more preferably 20 to 60 volume %, and even more preferably 25 to 50 volume %.

[0109] The photoelectric conversion film containing a specific compound is a non-luminescent film, and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode). A non-luminescent film 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.

[0110] <Dye> The photoelectric conversion film may further contain a dye in addition to the specific compound. The dye is a compound different from the above specific compound. The dye is preferably an organic dye. Examples of organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, Acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes and metal complex dyes, imidazoquinoxaline dyes described in WO2020 / 013246, WO2022 / 168856, JP2023-10305A, and JP2023-10299A, acceptor-donor-acceptor type dyes in which two acidic nuclei are bound to a donor, and donor-acceptor-donor type dyes in which two donors are bound to an acceptor. As the organic dye, a cyanine dye, an imidazoquinoxaline dye, or an acceptor-donor-acceptor type dye is preferable, because it has a maximum absorption wavelength in a preferred range described later.

[0111] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably from 400 to 700 nm, and even more preferably from 400 to 650 nm.

[0112] The dyes may be used alone or in combination of two or more. The content of the dye in the photoelectric conversion film relative to the total content of the specific compound and the dye (=(film thickness of the dye in monolayer equivalent / (film thickness of the specific compound in monolayer equivalent+film thickness of the dye in monolayer equivalent)×100) is preferably 15 to 75 volume %, more preferably 20 to 60 volume %, and even more preferably 20 to 50 volume %.

[0113] <Film formation method> The photoelectric conversion film may be formed, for example, by a dry film formation method. Examples of the dry film formation method include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), and CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and the vacuum deposition method is preferred. When forming the photoelectric conversion film by the vacuum deposition method, the manufacturing conditions such as the degree of vacuum and the deposition temperature can be set according to a conventional method.

[0114] The thickness of the photoelectric conversion film is preferably from 10 to 1000 nm, more preferably from 50 to 800 nm, and further preferably from 50 to 500 nm.

[0115] 〔electrode〕 The photoelectric conversion element preferably has an electrode. The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO: Indium Zinc Oxide); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and nanocarbon materials such as carbon nanotubes and graphene. In terms of high conductivity and transparency, conductive metal oxides are preferred.

[0116] Generally, when a conductive film is made thinner than a certain range, the resistance value often increases rapidly. In the solid-state imaging device incorporating the photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10,000 Ω / □, and there is a large degree of freedom in the range of the film thickness that can be thinned. Furthermore, the thinner the upper electrode (transparent conductive film) 15 is, the less light it absorbs, and generally the higher the light transmittance. An increase in light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in the transmittance that accompany a thinner film, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0117] The lower electrode 11 may be transparent or may be non-transparent and reflect light depending on the application. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine; metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (for example, titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and granphenes.

[0118] 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 of the method include an electron beam method, a sputtering method, a resistance heating deposition method, a chemical reaction method (such as a sol-gel method), and a method of applying a dispersion of indium tin oxide.

[0119] [Charge blocking film: electron blocking film, hole blocking film] The photoelectric conversion element preferably has one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film. The intermediate layer may be, for example, a charge blocking film. When the photoelectric conversion element has this film, the characteristics (quantum efficiency, response speed, etc.) of the obtained photoelectric conversion element are more excellent. The charge blocking film may be, for example, an electron blocking film and a hole blocking film.

[0120] [Electron blocking film] The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Furthermore, polymeric materials can also be used as the electron blocking film. Examples of the polymeric material include polymers of phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.

[0121] The electron blocking film may be made up 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, and the quantum efficiency is increased. Examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, copper gallium oxide, copper strontium oxide, niobium oxide, molybdenum oxide, copper indium oxide, silver indium oxide, and iridium oxide.

[0122] [Hole blocking film] The hole blocking film is an acceptor organic semiconductor material (compound), and the above-mentioned n-type organic semiconductor can be used. The hole blocking film may be made up of multiple films.

[0123] Examples of the manufacturing method of the charge blocking film include a dry film forming method and a wet film forming method. Examples of the dry film forming method include a vapor deposition method and a sputtering method. The vapor deposition method may be either a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, and a physical vapor deposition method such as a vacuum vapor deposition method is preferable. Examples of the wet film forming method include an inkjet method, a spray method, a nozzle print method, a spin coat method, a dip coat method, a cast method, a die coat method, a roll coat method, a bar coat method, and a gravure coat method, and the inkjet method is preferable in terms of high-precision patterning.

[0124] 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 further preferably from 5 to 30 nm.

[0125] 〔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. Regarding the position of the substrate, the conductive film, the photoelectric conversion film, and the transparent conductive film are usually laminated in this order on the substrate.

[0126] [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, etc. Therefore, the above-mentioned degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer such as ceramics such as dense metal oxides, metal nitrides, or metal nitride oxides that do not allow water molecules to penetrate, or diamond-like carbon (DLC). As for the sealing layer, for example, the description in paragraphs

[0210] to

[0215] of JP2011-082508A can be mentioned, the contents of which are incorporated herein by reference.

[0127] [Method of manufacturing photoelectric conversion element] The photoelectric conversion element can be produced by a known production method. Specifically, for example, there is mentioned a method for producing a photoelectric conversion element including 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 producing a photoelectric conversion element may include other steps in addition to those described above (for example, a step of forming a charge blocking film and a step of forming a sealing layer). The method for forming each layer is as described above.

[0128] [Image sensor] Photoelectric conversion elements are used, for example, as imaging elements. An imaging element is an element that converts the optical information of an image into an electrical signal, and is usually composed of multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal, and outputting the electrical signal pixel by pixel out of the imaging element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The method for producing the imaging element is not particularly limited, but may be a method including the step of producing the above-mentioned photoelectric conversion element.

[0129] [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 above-mentioned photoelectric conversion element may be used alone, or the above-mentioned photoelectric conversion element may be used as a line sensor arranged in a straight line or as a two-dimensional sensor arranged on a plane.

[0130] [Compound] The present invention also includes the invention of a compound. The compound of the present invention is the above-mentioned specific compound. EXAMPLES

[0131] The present invention will be described in further detail below with reference to examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0132] [Compounds used in photoelectric conversion films] The materials used in the photoelectric conversion film are listed below.

[0133] [Synthesis of compound (1-1)] Compound (1-1) was synthesized according to the following scheme.

[0134] [ka]

[0135] <Synthesis of compound (1-1-2)> Into a glass reaction vessel were placed 15.0 mmol of compound (1-1-1), 32.0 mmol of 2-formylfuran-5-boronic acid, 45 mmol of potassium carbonate, 80 mL of N,N-dimethylformamide, and 16 mL of water, and the atmosphere inside the vessel was replaced with nitrogen. 3.0 mmol of dichlorobis(triphenylphosphine)palladium(II) was further added to the reaction vessel and reacted at 80° C. for 5 hours. After cooling, water was added and the solid was filtered. The obtained solid was purified by silica gel column chromatography to obtain 5.9 mmol of compound (1-1-2) (yield 39%).

[0136] <Synthesis of compound (1-1)> In a glass reaction vessel, 2.0 mmol of the compound (1-1-2), 5.0 mmol of 1,3-dimethylbarbituric acid, 60 mL of toluene, and 0.4 mmol of piperidine were placed and reacted at 100° C. for 2 hours under a nitrogen atmosphere. The precipitated solid was filtered, and the obtained solid was washed successively with tetrahydrofuran (THF), dimethylacetamide, and THF, and then purified by sublimation to obtain 1.2 mmol of compound (1-1) (yield 61%). Since compound (1-1) has low solubility, the structure was confirmed by LDI-MS (laser desorption ionization mass spectrometry). The measurement results of LDI-MS of compound (1-1) are shown below. LDI-MS (compound (1-1)):658(M + )

[0137] The compounds of the Examples and Comparative Examples used in the photoelectric conversion film other than the compound (1-1) were synthesized according to the synthesis method of the compound (1-1).

[0138] [Specific compound] The specific compounds used in the photoelectric conversion film and the comparative compounds used as comparative examples are shown below. The compounds (1-1) to (1-8) and the compounds (2-1) to (2-4) are specific compounds, and the compound (C-1) is a comparative compound.

[0139] [ka]

[0140] [n-type organic semiconductor] Fullerene (C 60 )

[0141] [p-type organic semiconductor]

[0142] [ka]

[0143] [evaluation] The quantum efficiency, response speed, and electric field strength dependency of the response speed when the photoelectric conversion element received red light (wavelength 650 nm) were evaluated by the following methods.

[0144] [Fabrication of photoelectric conversion element] Using the various components shown above, a photoelectric conversion element was produced in the form shown in Fig. 2. Here, the photoelectric conversion element is composed of 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 deposited on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and a compound (EB-1) was deposited on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Next, with the glass substrate at room temperature, each specific compound or each comparative compound shown in Table 1 and an n-type organic semiconductor (fullerene (C 60 )) and the p-type organic semiconductor (D-1) were co-deposited by vacuum deposition to a thickness of 80 nm in terms of a single layer, thereby forming a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. At this time, the film formation speed of the photoelectric conversion film 12 was 1.0 Å / sec. Further, a compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After a SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, an aluminum oxide (Al2O3) layer was formed thereon by ALCVD (Atomic Layer Chemical Vapor Deposition), and the resulting laminate was heated at 150°C for 30 minutes in a glove box to obtain a photoelectric conversion element.

[0145] [ka]

[0146] [Dark current] For each of the obtained photoelectric conversion elements, the dark current was measured by the following method. The lower and upper electrodes of each photoelectric conversion element are each 5 A voltage was applied so that the electric field strength was 100 nA / cm, and the current value in the dark (dark current) was measured. As a result, the dark current was 50 nA / cm for all photoelectric conversion elements. 2 It was confirmed that the dark current was sufficiently low.

[0147] [Quantum efficiency] For each photoelectric conversion element, the quantum efficiency when red light was received was measured by the following method. Each photoelectric conversion element has a capacitance of 2.0×10 5 After applying a voltage to obtain an electric field strength of 10000 V / cm, the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 650 nm was evaluated by irradiating light from the upper electrode (transparent conductive film) side, 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 7)

[0148] 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

[0149] [Response speed] The response speed of each photoelectric conversion element when receiving red light was evaluated by the following method. Photoelectric conversion element: 2.0×10 5 A voltage was applied so that the intensity was 1000 V / cm. Then, an LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 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. It is preferable that the response speed is rated C or higher. Equation (S2): Relative response speed = (rise time of each photoelectric conversion element) / rise time of the photoelectric conversion element of Example 7)

[0150] A: Relative response speed is less than 0.75 B: Relative response speed is 0.75 or more and less than 1.5 C: Relative response speed is 1.5 or more and less than 2.5 D: Relative response speed is 2.5 or more

[0151] [Response speed dependence on electric field strength] For each photoelectric conversion element, the dependence of the response speed on the electric field strength when red light was received was evaluated by the following method. In the evaluation of the response speed above, the voltage applied to each photoelectric conversion element was set to 7.5×10 4 The same procedure was followed except that the voltage was changed to 7.5×10 4 The rise time in 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. Equation (S3): Dependence of response speed on electric field strength = (applied voltage of each photoelectric conversion element 7.5 × 10 4 V / cm) / (applied voltage of each photoelectric conversion element 2.0×10 5 Rise time in V / cm

[0152] A: The response speed depends on the electric field strength less than 3.0 B: The electric field strength dependence of the response speed is 3.0 or more and less than 4.0 C: The electric field strength dependence of the response speed is 4.0 or more and less than 5.0 D: Response time dependence on electric field strength is 5.0 or more

[0153] [result]

[0154] The evaluation results are shown in Table 1 below. In the table, the column "Substituent group P" indicates X for a specific compound. 1 -C(R c1 R c2 )-, R c1 and R c2 each independently represents a group selected from the substituent group P, or X 1 -Si(R c3 R c4 )-, Rc3 and R c4 are each independently a group selected from the substituent group P, they are represented as "A", and otherwise they are represented as "B". In the table, the column "Formula (A-3)" indicates the formula for a specific compound. 1 and A 2 is a group represented by formula (A-3), it is represented as "A", and in other cases it is represented as "B". In the table, the column "Formula (C-1) or Formula (C-2)" indicates the specific compound. 1 and A 2 are each independently a group represented by formula (C-1) or formula (C-2), it is represented as "A", and otherwise it is represented as "B".

[0155] [Table 1]

[0156] 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 electric field intensity dependency of the response speed. It was also confirmed that the photoelectric conversion element of the present invention has an excellent quantum efficiency when receiving red light. In addition, by comparing Example 6 and Example 7, it was found that the specific compound 1 and A 2 It has been confirmed that the effects of the present invention are more excellent when is a group represented by formula (A-3). From the comparison between Example 7 and Example 8, for a specific compound, A 1 and A 2 are each independently a group represented by formula (C-1) or formula (C-2), it has been confirmed that the quantum efficiency and the effects of the present invention are more excellent. From the comparison of Examples 9 to 12, X 1 -C(R c1 R c2 )-, R c1 and R c2 are each independently a group selected from the substituent group P, it has been confirmed that the quantum efficiency and the effects of the present invention are more excellent. [Explanation of symbols]

[0157] 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, The photoelectric conversion element, wherein the photoelectric conversion film contains a compound represented by formula (1). 【Chemistry 1】 In formula (1), X １ is -C(R ｃ１ R ｃ２ ) -, -Si(R ｃ３ R ｃ４ ) - or -Ge(R ｃ５ R ｃ６ )-. ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ , R ｃ５ and R ｃ６ each independently represents a hydrogen atom or a substituent. R ｃ１ and R ｃ２ , R ｃ３ and R ｃ４ , and R ｃ５ and R ｃ６ may be bonded to each other to form a ring which may have a substituent. R Ｚ１ and R Ｚ２ each independently represents a hydrogen atom or a substituent. Y １ and Y ２ each independently represents an aromatic ring which may have a substituent. R １ and R ２ each independently represents a hydrogen atom or a substituent. A １ and A ２ each independently represents a group represented by formula (A-1) or formula (A-2). In formula (A-1), C １ represents a ring containing two or more carbon atoms which may have a substituent. W 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), R ｂ１ and R ｂ２ each independently represents a cyano group, -COOR ｂ３ , -COR ｂ４ , or -SO ２ R ｂ５ Represents ｂ３ , R ｂ４ and R ｂ５ 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. * indicates the bond position.

2. 2. The photoelectric conversion element according to claim 1, wherein the compound represented by formula (1) is a compound represented by any one of formulas (2) to (4). 【Chemistry 2】 In formulas (2) to (4), X ２ and X ３ each independently represents an oxygen atom, a sulfur atom, or -NR ３ - or a selenium atom. Z １ ~Z １２ are each independently: =CR ４ - or a nitrogen atom. R ３ and R ４ each independently represents a hydrogen atom or a substituent. X １ , R Ｚ１ , R Ｚ２ , R １ , R ２ , A １ and A ２ is X in the formula (1). １ , R Ｚ１ , R Ｚ２ , R １ , R ２ , A １ and A ２ is synonymous with.

3. R ｃ１ and R ｃ２ At least one of represents a group selected from the substituent group S; R ｃ３ and R ｃ４ At least one of the following represents a group selected from the substituent group S; R ｃ５ and R ｃ６ The photoelectric conversion element according to claim 1 , wherein at least one of the following groups represents a group selected from the substituent group S: Substituent group S: an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and an aliphatic heterocyclic group which may have a substituent.

4. X １ -C(R ｃ１ R ｃ２ )-, R ｃ１ and R ｃ２ each independently represents a group selected from the substituent group S; X １ -Si(R ｃ３ R ｃ４ )-, R ｃ３ and R ｃ４ The photoelectric conversion element according to claim 3 , wherein each independently represents a group selected from the substituent group S.

5. X １ -C(R ｃ１ R ｃ２ )-, R ｃ１ and R ｃ２ each independently represents a group selected from the substituent group P; X １ -Si(R ｃ３ R ｃ４ )-, R ｃ３ and R ｃ４ The photoelectric conversion element according to claim 4 , wherein each independently represents a group selected from the substituent group P. Substituent group P: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 5 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, and phenyl groups which may have a substituent.

6. Y １ and Y ２ The photoelectric conversion element according to claim 1 , wherein each independently represents an aromatic ring which may have a halogen atom.

7. 2. The photoelectric conversion element according to claim 1, wherein the group represented by formula (A-1) is a group represented by formula (A-3). 【Chemistry 3】 In formula (A-3), C ２ represents a ring containing 3 or more carbon atoms which may have a substituent. W 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. * indicates the bond position.

8. A １ and A ２ The photoelectric conversion element according to any one of claims 1 to 7, wherein each of the following independently represents a group represented by formula (C-1) or formula (C-2): 【Chemistry 4】 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 Represents. C ３ represents an aromatic ring which may have a substituent. 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 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 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. R ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent. * indicates the bond position.

9. the photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion element according to any one of claims 1 to 7, wherein 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.

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

11. The photoelectric conversion element according to any one of claims 1 to 7, wherein the photoelectric conversion film further contains a p-type organic semiconductor.

12. The photoelectric conversion element according to any one of claims 1 to 7, wherein the photoelectric conversion film further contains a dye.

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

14. An imaging device comprising the photoelectric conversion element according to any one of claims 1 to 7.

15. An optical sensor comprising the photoelectric conversion element according to any one of claims 1 to 7.

16. A method for manufacturing an imaging element, comprising the step of manufacturing the photoelectric conversion element according to any one of claims 1 to 7.

17. A compound represented by formula (1). 【Chemistry 5】 In formula (1), X １ is -C(R ｃ１ R ｃ２ ) -, -Si(R ｃ３ R ｃ４ ) - or -Ge(R ｃ５ R ｃ６ )-. ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ , R ｃ５ and R ｃ６ each independently represents a hydrogen atom or a substituent. R ｃ１ and R ｃ２ , R ｃ３ and R ｃ４ , and R ｃ５ and R ｃ６ may be bonded to each other to form a ring which may have a substituent. R Ｚ１ and R Ｚ２ each independently represents a hydrogen atom or a substituent. Y １ and Y ２ each independently represents an aromatic ring which may have a substituent. R １ and R ２ each independently represents a hydrogen atom or a substituent. A １ and A ２ each independently represents a group represented by formula (A-1) or formula (A-2). In formula (A-1), C １ represents a ring containing two or more carbon atoms which may have a substituent. W 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 R 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), R ｂ１ and R ｂ２ each independently represents a cyano group, -COOR ｂ３ , -COR ｂ４ , or -SO ２ R ｂ５ Represents ｂ３ , R ｂ４ and R ｂ５ 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. * indicates the bond position.

18. The compound according to claim 17, wherein the compound represented by formula (1) is a compound represented by any one of formulas (2) to (4). 【Chemistry 6】 In formulas (2) to (4), X ２ and X ３ each independently represents an oxygen atom, a sulfur atom, or -NR ３ - or a selenium atom. Z １ ~Z １２ are each independently: =CR ４ - or a nitrogen atom. R ３ and R ４ each independently represents a hydrogen atom or a substituent. X １ , R Ｚ１ , R Ｚ２ , R １ , R ２ , A １ and A ２ is X in the formula (1). １ , R Ｚ１ , R Ｚ２ , R １ , R ２ , A １ and A ２ is synonymous with.

19. R ｃ１ and R ｃ２ At least one of represents a group selected from the substituent group S; R ｃ３ and R ｃ４ At least one of the following represents a group selected from the substituent group S; R ｃ５ and R ｃ６ The compound according to claim 17, wherein at least one of the following represents a group selected from the substituent group S. Substituent group S: an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and an aliphatic heterocyclic group which may have a substituent.

20. X １ -C(R ｃ１ R ｃ２ )-, R ｃ１ and R ｃ２ each independently represents a group selected from the substituent group S; X １ -Si(R ｃ３ R ｃ４ )-, R ｃ３ and R ｃ４ Each of the groups independently represents a group selected from the group S of substituents.

21. X １ -C(R ｃ１ R ｃ２ )-, R ｃ１ and R ｃ２ each independently represents a group selected from the substituent group P; X １ -Si(R ｃ３ R ｃ４ )-, R ｃ３ and R ｃ４ Each of the groups independently represents a group selected from the group P of substituents. Substituent group P: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 5 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, and phenyl groups which may have a substituent.

22. Y １ and Y ２ The compound according to claim 17 , wherein each independently represents an aromatic ring optionally having a halogen atom.

23. The compound according to claim 17, wherein the group represented by formula (A-1) is a group represented by formula (A-3). 【Chemistry 7】 In formula (A-3), C ２ represents a ring containing 3 or more carbon atoms which may have a substituent. W 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. * indicates the bond position.

24. A １ and A ２ are each independently a group represented by formula (C-1) or formula (C-2). 【Chemistry 8】 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 Represents. C ３ represents an aromatic ring which may have a substituent. 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 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. R ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent. * indicates the bond position.

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