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

Abstract

Provided is a photoelectric conversion element having excellent quantum efficiency when receiving blue light. Also provided are an imaging element, an optical sensor, and a compound relating to the photoelectric conversion element. This photoelectric conversion element has 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). And D represents a group represented by any of formulae (2) to (5). A1 and A2 each independently represent a group represented by formula (A-1).

Description

Technical Field

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

[0002] In recent years, development of elements having a photoelectric conversion film (for example, an imaging element) has been underway.

[0003] For example, Patent Document 1 discloses a photoelectric conversion element containing a specific compound as an electron acceptor material.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: WO 2014 / 026224

[0007] In recent years, with the demand for improving the performance of imaging elements and light sensors, etc., there has also been a demand for further improving various characteristics required for the photoelectric conversion elements used in these.

[0008] For example, when the photoelectric conversion element receives blue light (in particular, light having a wavelength of 460 nm), a higher level of quantum efficiency is required. Herein, the above-mentioned blue light refers to light in the wavelength range of 400 to 500 nm.

[0009] As a result of the present inventors' research on a photoelectric conversion element containing the compound disclosed in Patent Document 1, it has been found that there is still room for further improvement in the quantum efficiency when receiving the above-mentioned blue light. Summary of the Invention

[0010] Technical Problem to be Solved by the Invention

[0011] Therefore, an object of the present invention is to provide a photoelectric conversion element having excellent quantum efficiency when receiving blue light.

[0012] Furthermore, an object of the present invention is also to provide an imaging element, a light sensor, a method for manufacturing an imaging element, and a compound related to the above-mentioned photoelectric conversion element. Means for Solving the Technical Problem

[0013] As a result of the present inventors' intensive research to solve the above-mentioned problems, the present invention has been completed. That is, it has been found that the above-mentioned problems can be solved by the following structure.

[0014] 〔1〕A photoelectric conversion element having, in this order, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein

[0015] the above-mentioned photoelectric conversion film contains a compound represented by the following formula (1).

[0016] 〔2〕The photoelectric conversion element according to 〔1〕, wherein,

[0017] R Y1 represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group or a halogen atom.

[0018] 〔3〕The photoelectric conversion element according to 〔1〕 or 〔2〕, wherein,

[0019] D represents a group represented by any one of the following formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (3-10), formula (3-11), formula (3-12), formula (3-13), formula (4-10), formula (4-11), formula (5-10) and formula (5-11).

[0020] 〔4〕The photoelectric conversion element according to any one of 〔1〕 to 〔3〕, wherein,

[0021] Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkynyl group having 2 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group or a halogen atom.

[0022] 〔5〕The photoelectric conversion element according to 〔3〕, wherein,

[0023] D represents a group represented by any one of the above formula (2-10), the above formula (2-11), the above formula (2-12), the above formula (2-13), the above formula (3-10), the above formula (3-11), the above formula (3-12), the above formula (3-13), the above formula (5-10) and the above formula (5-11).

[0024] 〔6〕The photoelectric conversion element according to any one of 〔1〕 to 〔5〕, wherein,

[0025] W 1 is an oxygen atom or a sulfur atom.

[0026] 〔7〕The photoelectric conversion element according to any one of 〔1〕to 〔6〕, wherein,

[0027] The group represented by the above formula (A-1) is the group represented by the following formula (A-2).

[0028] 〔8〕The photoelectric conversion element according to 〔7〕, wherein,

[0029] The group represented by the above formula (A-2) is the group represented by the following formula (C-1) or the group represented by the following formula (C-2).

[0030] 〔9〕The photoelectric conversion element according to 〔8〕, wherein,

[0031] X c1 and X c2 are both oxygen atoms, and X c3 and X c4 are both oxygen atoms.

[0032] 〔10〕The photoelectric conversion element according to any one of 〔1〕to 〔9〕, wherein,

[0033] Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, a silyl group which may have a substituent or a halogen atom.

[0034] 〔11〕The photoelectric conversion element according to 〔3〕, wherein,

[0035] D represents the group represented by the above formula (4-10) or the group represented by the above formula (4-11).

[0036] 〔12〕The photoelectric conversion element according to 〔11〕, wherein,

[0037] Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent or the group represented by the following formula (S1).

[0038] 〔13〕The photoelectric conversion element according to any one of 〔1〕to 〔12〕, wherein,

[0039] The above-mentioned photoelectric conversion film further contains an n-type organic semiconductor,

[0040] The above-mentioned photoelectric conversion film has a bulk heterojunction structure formed in a state where the compound represented by the above formula (1) is mixed with the above-mentioned n-type organic semiconductor.

[0041] 〔14〕The photoelectric conversion element according to 〔13〕, wherein

[0042] The above-mentioned n-type organic semiconductor includes fullerenes selected from the group consisting of fullerenes and their derivatives.

[0043] 〔15〕The photoelectric conversion element according to any one of 〔1〕 to 〔14〕, wherein

[0044] The above-mentioned photoelectric conversion film further contains a p-type organic semiconductor.

[0045] 〔16〕The photoelectric conversion element according to any one of 〔1〕 to 〔15〕, wherein

[0046] The above-mentioned photoelectric conversion film further contains a pigment.

[0047] 〔17〕The photoelectric conversion element according to any one of 〔1〕 to 〔16〕, wherein

[0048] Between the above-mentioned conductive film and the above-mentioned transparent conductive film, there is one or more intermediate layers in addition to the above-mentioned photoelectric conversion film.

[0049] 〔18〕An imaging element having the photoelectric conversion element according to any one of 〔1〕 to 〔17〕.

[0050] 〔19〕An optical sensor having the photoelectric conversion element according to any one of 〔1〕 to 〔17〕.

[0051] 〔20〕A method for manufacturing an imaging element, which includes a step of manufacturing the photoelectric conversion element according to any one of 〔1〕 to 〔17〕.

[0052] 〔21〕A compound represented by the following formula (1).

[0053] 〔22〕The compound according to 〔21〕, wherein

[0054] R Y1 represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group or a halogen atom.

[0055] 〔23〕The compound according to 〔21〕 or 〔22〕, wherein

[0056] D represents a group represented by any one of the following formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (4-10), (4-11), (5-10), and (5-11).

[0057] 〔24〕The compound according to any one of 〔21〕 to 〔23〕, wherein,

[0058] Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkynyl group having 2 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group or a halogen atom.

[0059] 〔25〕The compound according to 〔23〕, wherein,

[0060] D represents a group represented by any one of the above formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (5-10), and (5-11).

[0061] 〔26〕The compound according to any one of 〔21〕 to 〔25〕, wherein,

[0062] W 1 is an oxygen atom or a sulfur atom.

[0063] 〔27〕The compound according to any one of 〔21〕 to 〔26〕, wherein,

[0064] The group represented by the above formula (A-1) is the group represented by the following formula (A-2).

[0065] 〔28〕The compound according to 〔27〕, wherein,

[0066] The group represented by the above formula (A-2) is the group represented by the following formula (C-1) or the group represented by the following formula (C-2).

[0067] 〔29〕The compound according to 〔28〕, wherein,

[0068] X c1 and X c2 are both oxygen atoms, and X c3 and X c4 are both oxygen atoms.

[0069] 〔30〕The compound according to any one of 〔21〕to 〔29〕, wherein,

[0070] Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, a silyl group which may have a substituent, or a halogen atom.

[0071] 〔31〕The compound according to 〔23〕, wherein,

[0072] D represents a group represented by the above formula (4-10) or a group represented by the above formula (4-11).

[0073] 〔32〕The compound according to 〔31〕, wherein,

[0074] Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, or a group represented by the following formula (S1).

[0075] Advantages of the Invention

[0076] According to the present invention, a photoelectric conversion element having excellent quantum efficiency when receiving blue light can be provided.

[0077] Moreover, according to the present invention, an imaging element, a light sensor, a method for manufacturing an imaging element, and a compound related to the above photoelectric conversion element can be provided. Brief Description of the Drawings

[0078] Figure 1 is a cross-sectional schematic view showing a structural example of a photoelectric conversion element.

[0079] Figure 2 is a cross-sectional schematic view showing a structural example of a photoelectric conversion element. Detailed Description of the Invention

[0080] Hereinafter, the present invention will be described in detail.

[0081] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0082] Hereinafter, the meanings of the respective descriptions in this specification are shown.

[0083] In this specification, the numerical range represented by "~" means the range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0084] In this specification, a hydrogen atom can be a light hydrogen atom (ordinary hydrogen atom) and a deuterium atom (for example, dihydrogen atom, etc.).

[0085] In this specification, regarding a compound that can have geometric isomers (cis-trans isomers), for the sake of convenience in description, the general formula or structural formula representing the above compound is sometimes described only in either the cis form or the trans form. Even in such a case, unless otherwise specifically stated, the form of the above compound is not limited to either the cis form or the trans form, and the above compound can also be in either the cis form or the trans form.

[0086] Unless otherwise specifically stated, the bonding direction of the divalent group (for example, -CO-O-, etc.) described in this specification is not limited. For example, when Y in the compound represented by the formula "X-Y-Z" is -CO-O-, the above compound can be either "X-O-CO-Z" or "X-CO-O-Z".

[0087] Unless otherwise specifically stated, the symbol "*" explicitly shown in the chemical formula represents the bonding position.

[0088] In this specification, when there are multiple substituents, linking groups, etc. represented by specific symbols (hereinafter, also referred to as "substituents, etc.") or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. can be the same as or different from each other. This also applies to the specification of the number of substituents, etc.

[0089] In this specification, unless otherwise specifically stated, "substituent" can include the groups exemplified in the following substituent W.

[0090] (Substituent W)

[0091] The substituent W in this specification is described.

[0092] Regarding the substituent W, 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 heteroepoxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a primary amino group, a secondary amino group, or a tertiary amino group (including an anilino group), an alkylthio group, an arylthio group, a heterocyclicthio 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 imide group, a phosphino group, an oxyphosphino group, an oxyphosphinoxy group, an oxyphosphinoamino group, a phosphinyl group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, and a boronic acid group can be mentioned.

[0093] Further, when possible, each of the above groups may also have a substituent (e.g., one or more groups among the above groups, etc.). For example, an alkyl group that may have a substituent may also be included as one form of the substituent W.

[0094] Further, when the substituent W has a carbon atom, the number of carbon atoms of the substituent W is, for example, 1 to 20.

[0095] The number of atoms other than hydrogen atoms of the substituent W is, for example, 1 to 30.

[0096] In addition, the specific compounds described later are also preferably free of a carboxyl group, a salt of a carboxyl group, a salt of a phosphoric acid group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxyl 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 substituents.

[0097] In the present specification, the aliphatic hydrocarbon group may be linear, branched, or cyclic.

[0098] Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

[0099] In the present specification, unless otherwise specifically stated, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6.

[0100] The alkyl group may be linear, branched, or cyclic.

[0101] Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-hexyl group, and a cyclopentyl group.

[0102] Further, the alkyl group may be any of a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, and may also have their ring structure as a partial structure.

[0103] In the alkyl group which may have substituents, as the substituents which the alkyl group may have, for example, the groups exemplified in Substituent W can be cited. Among them, an aryl group (preferably having 6 to 18 carbon atoms, more preferably 6 carbon atoms), a heteroaryl group (preferably having 5 to 18 carbon atoms, more preferably 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom) is preferred.

[0104] In this specification, unless otherwise specifically stated, the alkyl part in the alkoxy group is preferably the above alkyl group. The alkyl part in the alkylthio group is preferably the above alkyl group.

[0105] In the alkoxy group which may have substituents, examples of the substituents which the alkoxy group may have are the same as those of the substituents in the alkyl group which may have substituents. In the alkylthio group which may have substituents, examples of the substituents which the alkylthio group may have are the same as those of the substituents in the alkyl group which may have substituents.

[0106] In this specification, unless otherwise specifically stated, the alkenyl group can be any of linear, branched, and cyclic. The number of carbon atoms of the above alkenyl group is preferably 2 to 20. In the alkenyl group which may have substituents, examples of the substituents which the alkenyl group may have are the same as those of the substituents in the alkyl group which may have substituents.

[0107] In this specification, unless otherwise specifically stated, the alkynyl group can be any of linear, branched, and cyclic. The number of carbon atoms of the above alkynyl group is preferably 2 to 20. In the alkynyl group which may have substituents, examples of the substituents which the alkynyl group may have are the same as those of the substituents in the alkyl group which may have substituents.

[0108] In this specification, unless otherwise specifically stated, the aromatic ring or the aromatic ring constituting the aromatic ring group can be any of monocyclic and polycyclic (for example, 2 to 6 rings, etc.). The monocyclic aromatic ring is an aromatic ring having only one ring structure as the ring structure. The polycyclic (for example, 2 to 6 rings, etc.) aromatic ring is an aromatic ring formed by condensing a plurality of (for example, 2 to 6, etc.) aromatic ring structures as the ring structure.

[0109] The number of ring atoms of the above aromatic ring is preferably 4 to 15.

[0110] The above aromatic ring can be an aromatic hydrocarbon ring and an aromatic heterocycle.

[0111] When the above aromatic ring is an aromatic heterocycle, the number of heteroatoms possessed by the ring atoms is, for example, 1 to 10. As the above heteroatoms, for example, 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 can be cited.

[0112] As the above aromatic hydrocarbon ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring can be cited.

[0113] As the above aromatic heterocycle, for example, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (e.g., 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring, etc.), a tetrazine ring (e.g., 1,2,4,5-tetrazine ring, etc.), 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 naphthimidazole ring, a naphthoxazole ring, a pyrrolobenzimidazole ring (e.g., 5H-pyrrolo[1,2-a]imidazole ring, etc.), an imidazolooxazole ring (e.g., imidazo[2,1-b]oxazole ring, etc.), a thiophenothiazole ring (e.g., thiopheno[2,3-d]thiazole ring, etc.), a benzothiadiazole ring, a benzodithiophene ring (e.g., benzo[1,2-b:4,5-b']dithiophene ring, etc.), a thiophenothiophene ring (e.g., thiopheno[3,2-b]thiophene ring, etc.), a thiazolothiazole ring (e.g., thiazolo[5,4-d]thiazole ring, etc.), a 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-dithiabicyclopent[b,g]naphthalene ring, etc.), a benzothiophenobenzothiophene ring, a dithieno[3,2-b:2',3'-d]thiophene ring, and a 3,4,7,8-tetrathiabicyclopenta[a,e]cyclopentadiene ring.

[0114] In an aromatic ring that may have a substituent, examples of the types of substituents that the aromatic ring can have include the groups exemplified in substituent W. The number of substituents when the above aromatic ring has a substituent may be 1 or more (e.g., 1 to 4, etc.).

[0115] In this specification, in the case of an aromatic ring group, for example, a group formed by removing 1 or more (e.g., 1 to 5, etc.) hydrogen atoms from the above aromatic ring can be cited.

[0116] In this specification, in the case of an aryl group, for example, a group formed by removing 1 hydrogen atom from the ring corresponding to the aromatic hydrocarbon ring in the above aromatic ring can be cited.

[0117] In this specification, in the case of a heteroaryl group, for example, a group formed by removing 1 hydrogen atom from the ring corresponding to the aromatic heterocycle in the above aromatic ring can be cited.

[0118] In the present specification, in the case of an arylene group, for example, a group formed by removing two hydrogen atoms from the ring corresponding to the aromatic hydrocarbon ring in the above aromatic ring can be exemplified.

[0119] In the present specification, in the case of a heteroarylene group, for example, a group formed by removing two hydrogen atoms from the ring corresponding to the aromatic heterocycle in the above aromatic ring can be exemplified.

[0120] Among 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 substituents that these groups may have can be exemplified by the groups exemplified in the substituent W. When these groups which may have a substituent have a substituent, the number of substituents may be 1 or more (for example, 1 to 4, etc.).

[0121] In the present specification, the number of ring atoms of the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and further preferably 6 to 8.

[0122] As the heteroatom contained in the above aliphatic heterocyclic group, for example, 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 can be exemplified, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferred.

[0123] As the aliphatic heterocycle constituting the above aliphatic heterocyclic group, for example, a pyrrolidine ring, an oxolane, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, and γ-butyrolactone can be exemplified.

[0124] [Photoelectric conversion element]

[0125] The photoelectric conversion element of the present invention sequentially has a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein the above photoelectric conversion film contains a compound represented by the following formula (1) (hereinafter, also referred to as "specific compound").

[0126] Although the mechanism by which the problems of the present invention can be solved by adopting the above structure in the photoelectric conversion element of the present invention is not necessarily clear, the inventors etc. presume as follows.

[0127] In addition, there is no limitation on the mechanism by which the effects can be obtained by the following presumption. That is, even in the case where the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention.

[0128] Generally, it is considered that, like the specific compound of the present invention, for an A-D-A type pigment in which a receptor is directly bonded to a donor having a 2-fused ring structure, since the conjugated system is short, the absorbance usually becomes small, and thus it is not preferable if a high quantum efficiency is to be obtained.

[0129] However, as a result of the inventors' comprehensive research on A-D-A type pigments, it was unexpectedly confirmed that even for an A-D-A type pigment in which a receptor is directly bonded to a donor having a 2-fused ring structure, a high quantum efficiency can be obtained, and effective absorption is also shown in the short wavelength region (around 400 to 500 nm).

[0130] As described above, as a factor for obtaining a high quantum efficiency, the inventors speculated that although the absorbance of the molecule itself is not high, since its molecular weight is low, when a specific compound is formed into a photoelectric conversion film, the amount of substance per unit volume of the film can be increased.

[0131] Furthermore, the inventors speculated that by introducing appropriate substituents into the above-mentioned donor structure having a 2-fused ring structure, aggregation of A-D-A type pigments with each other can be suppressed, and effective electron or hole transfer can be achieved. As a result, compared with the photoelectric conversion element described in Patent Document 1 that does not have a substituent at the donor site, a higher quantum efficiency can be realized.

[0132] Hereinafter, a case where the quantum efficiency is more excellent when the photoelectric conversion element receives blue light (light within the wavelength range of 400 to 500 nm) is also referred to as the effect of the present invention being more excellent.

[0133] Hereinafter, the structure of the photoelectric conversion element of the present invention will be described in detail.

[0134] In Figure 1 FIG. shows a cross-sectional schematic view of an embodiment of the photoelectric conversion element of the present invention.

[0135] Figure 1 The photoelectric conversion element 10a shown has a structure in which a conductive film (hereinafter, also referred to as "lower electrode") 11 that functions 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 "upper electrode") 15 that functions as an upper electrode are laminated in this order.

[0136] In Figure 2 FIG. shows a structural example of another photoelectric conversion element. Figure 2 The photoelectric conversion element 10b shown has a structure 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 the lower electrode 11. In addition,[[]] Figure 1 and Figure 2 The lamination order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in

[0137] 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.

[0138] Moreover, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. At this time, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 -5 ~1×10 7 V / cm is applied between the pair of electrodes. In terms of performance and power consumption, as the applied voltage, 1×10 -4 ~1×10 7 V / cm is more preferable, and 1×10 -3 ~5×10 6 V / cm is further preferable.

[0139] In addition, regarding the voltage application method, in Figure 1 and Figure 2 , it is preferable to apply the voltage such that the side of the electron blocking film 16A becomes the cathode and the side of the photoelectric conversion film 12 becomes the anode. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or is assembled in an imaging element, the voltage can also be applied by the same method.

[0140] As described in detail in the later part, the photoelectric conversion element 10a (or 10b) can be preferably applied to the use in an imaging element.

[0141] Hereinafter, the forms of the respective layers constituting the photoelectric conversion element of the present invention will be described in detail.

[0142] 〔Photoelectric conversion film〕

[0143] The photoelectric conversion element of the present invention has a photoelectric conversion film.

[0144] <Specific compound>

[0145] The above-mentioned photoelectric conversion film contains a compound (specific compound) represented by the formula (1).

[0146] [Chemical formula 1]

[0147]

[0148] In the formula (1), D represents a group represented by any one of the formulas (2) to (5).

[0149] In the formulas (2) to (5), X 21 , X 31 , X 41 , X 42 , X 51 and X 52Each independently represents a sulfur atom, an oxygen atom, NR X1 or CR X2 R X3 .

[0150] R X1 ~R X3 Each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent,

[0151] R X2 and R X3 may be connected via a single bond or a divalent linking group. As the divalent linking group, for example, an alkylene group and -O- can be mentioned.

[0152] In formula (1), in terms of the aspect where the effects of the present invention are more excellent, D is preferably a group represented by formula (2), formula (3) or formula (5), and more preferably a group represented by formula (2).

[0153] In formulas (2) to (5), X 21 , X 31 , X 41 , X 42 , X 51 and X 52 are preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom.

[0154] As the aliphatic hydrocarbon group which may have a substituent represented by the above R X1 ~R X3 , for example, an alkyl group, an alkenyl group and an alkynyl group can be mentioned. The number of carbon atoms of the above aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 or 2. As the substituent which the aliphatic hydrocarbon group may have, for example, the groups exemplified in the above substituent W can be mentioned.

[0155] As the aliphatic hydrocarbon group which may have a substituent, among them, a linear or branched alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group or an isopropyl group is more preferred.

[0156] And, the specific forms of the aromatic ring group which may have a substituent represented by R X1 ~R X3 are as described above. For example, an aryl group which may have a substituent and a heteroaryl group which may have a substituent can be mentioned. As the substituent which the aromatic ring group may have, the groups exemplified in the above substituent W can be mentioned. As the substituent which the aromatic ring group may have, a methyl group is preferred.

[0157] As the R X1 ~R X3An aromatic ring group which may have substituents, preferably an aryl group having 6 to 14 carbon atoms which may have substituents or a heteroaryl group having 2 to 14 carbon atoms which may have substituents, more preferably a phenyl group.

[0158] In formulas (2) to (5), Y 21 , Y 22 , Y 23 , Y 24 , Y 31 , Y 32 , Y 33 , Y 34 , Y 41 , Y 42 , Y 51 and Y 52 each independently represents -CR Y1 = or a nitrogen atom. R Y1 represents a hydrogen atom or a substituent,

[0159] wherein, in formula (2), at least one of Y 21 to Y 24 represents -CRs=, in formula (3), at least one of Y 31 to Y 34 represents -CRs=, in formula (4), at least one of Y 41 and Y 42 represents -CRs=, in formula (5), at least one of Y 51 and Y 52 represents -CRs=.

[0160] The above Rs represents an alkyl group which may have substituents, an alkenyl group which may have substituents, an alkynyl group which may have substituents, an aryl group which may have substituents, a heteroaryl group which may have substituents, an alkoxy group which may have substituents, an aryloxy group which may have substituents, an amino group which may have substituents, a silyl group which may have substituents, a cyano group or a halogen atom.

[0161] As R Y1 , a hydrogen atom is preferred.

[0162] The substituents represented by R Y1 are not particularly limited, and for example, the groups exemplified in the above substituent W can be cited. As the substituents represented by R Y1The substituents represented, preferably include alkyl which may have substituents, alkenyl which may have substituents, alkynyl which may have substituents, aryl which may have substituents, heteroaryl which may have substituents, alkoxy which may have substituents, aryloxy which may have substituents, amino which may have substituents, silyl which may have substituents, cyano or a halogen atom, more preferably alkyl which may have substituents, aryl which may have substituents, heteroaryl which may have substituents, alkoxy which may have substituents, silyl which may have substituents or a halogen atom.

[0163] The substituents represented by R Y1 The further preferred modes of the substituents represented are the same as the preferred modes of the respective groups represented by Rs described below.

[0164] In formula (2), preferably at least one of Y 21 ~Y 24 represents -CR Y1 =, more preferably at least two represent -CR Y1 =, further preferably at least three represent -CR Y1 =, particularly preferably Y 21 ~Y 24 all represent -CR Y1 =.

[0165] In formula (3), preferably at least one of Y 31 ~Y 34 represents -CR Y1 =, more preferably at least two represent -CR Y1 =, further preferably at least three represent -CR Y1 =, particularly preferably Y 31 ~Y 34 all represent -CR Y1 =.

[0166] In formula (4), preferably at least one of Y 41 and Y 42 represents -CR Y1 =, more preferably Y 41 and Y 42 both represent -CR Y1 =.

[0167] In formula (5), preferably at least one of Y 51 and Y 52 represents -CR Y1 =, more preferably Y 51 and Y 52 both represent -CR Y1 =.

[0168] In formula (2), preferably Y 21 ~Y24 One or two of them represent -CRs=, and more preferably one represents -CRs=.

[0169] In formula (3), preferably one of Y 31 ~Y 34 represents -CRs=, and more preferably one represents -CRs=.

[0170] In formula (4), preferably one of Y 41 and Y 42 represents -CRs=, and more preferably Y 41 and Y 42 represents -CRs=.

[0171] In formula (5), preferably one of Y 51 and Y 52 represents -CRs=, and more preferably Y 51 and Y 52 represents -CRs=.

[0172] In addition, when calculating the number of -CRs= as described above, if the groups represented by Y 21 ~Y 24 , Y 31 ~Y 34 , Y 41 and Y 42 , and Y 51 and Y 52 can correspond to both -CR Y1 = and CRs=, then it is counted as -CRs=. For example, when two of Y 41 and Y 42 are -CCH3=, -CCH3= can correspond to both -CR Y1 = and CRs=, but it is counted as having two -CRs=. In other words, if one of the two -CCH3= corresponds to -CR Y1 = and the other corresponds to -CRs=, the number of -CRs= is not counted as one.

[0173] As described above, the above Rs represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an amino group that may have a substituent, a silyl group that may have a substituent, a cyano group or a halogen atom.

[0174] The alkyl group that may have a substituent represented by Rs can be any of linear, branched and cyclic.

[0175] When the above alkyl group is a linear alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 or 2.

[0176] When the above alkyl group is a branched alkyl group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 7.

[0177] When the above alkyl group is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6.

[0178] Moreover, as substituents which the above alkyl group may have, for example, groups exemplified in the above substituent W can be cited. As substituents which the alkyl group may have, a halogen atom is preferred, and a fluorine atom is more preferred. The alkyl group may be a perfluoroalkyl group such as trifluoromethyl.

[0179] The alkenyl group which may have substituents represented by Rs may be any of linear, branched and cyclic.

[0180] The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 5.

[0181] Moreover, as substituents which the above alkenyl group may have, for example, groups exemplified in the above substituent W can be cited. As substituents which the alkenyl group may have, an aryl group is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred, and a phenyl group is still more preferred.

[0182] As the alkenyl group, preferably, it is vinyl, a group formed by removing the hydrogen atom at the 2-position of propene or a group formed by removing the hydrogen atom at the 1-position of isobutene.

[0183] As substituents which the alkynyl group which may have substituents represented by Rs may have, for example, groups exemplified in the above substituent W can be cited. As substituents which the alkynyl group may have, an aryl group having 6 to 10 carbon atoms is preferred, and a phenyl group is still more preferred.

[0184] The number of carbon atoms of the alkynyl group is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 5.

[0185] As the alkynyl group which may have substituents, preferably, it is propargyl, 1-methylpropargyl or phenylacetylene.

[0186] The aryl group which may have substituents represented by Rs is not particularly limited and may be either monocyclic or polycyclic.

[0187] The number of carbon atoms of the above aryl group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.

[0188] As substituents that the above aryl group may have, for example, the groups exemplified in the above substituent W can be cited. As substituents that the aryl group may have, a halogen atom, an alkyl group, and an alkoxy group can be cited. The specific forms of the above groups are as described above. As substituents that the aryl group may have, a methyl group, an isopropyl group, or a methoxy group is preferred.

[0189] The heteroaryl group represented by Rs that may have a substituent is not particularly limited and can be either a monocyclic or polycyclic group.

[0190] The specific examples of the aromatic heterocycle constituting the above heteroaryl group are as described above.

[0191] The number of carbon atoms of the above heteroaryl group is preferably 2 to 20, more preferably 2 to 14, and further preferably 2 to 10. And, the number of heteroatoms that the heteroaryl group has is preferably 1 to 10, more preferably 1 to 3, and further preferably 1 or 2.

[0192] As substituents that the above heteroaryl group may have, for example, the groups exemplified in the above substituent W can be cited. As substituents that the heteroaryl group may have, a halogen atom, an alkyl group, and an alkoxy group can be cited. The specific forms of the above groups are as described above. As substituents that the heteroaryl group may have, a methyl group, an isopropyl group, or a methoxy group is preferred.

[0193] In the alkoxy group represented by Rs that may have a substituent, the alkyl group bonded to the oxygen atom can be any of linear, branched, and cyclic.

[0194] When the above alkyl group is a linear alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 or 2.

[0195] When the above alkyl group is a branched alkyl group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 7.

[0196] When the above alkyl group is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6.

[0197] As substituents that the alkoxy group may have, for example, the groups exemplified in the above substituent W can be cited.

[0198] In the aryloxy group represented by Rs that may have a substituent, the aryl group bonded to the oxygen atom is not particularly limited and can be either a monocyclic or polycyclic group.

[0199] The number of carbon atoms of the above aryl group is preferably 6 to 20, more preferably 6 to 14, and further preferably 6 to 10.

[0200] As substituents that the above aryl group may have, for example, the groups exemplified in the above substituent W can be cited. As substituents that the aryl group may have, a halogen atom, an alkyl group, and an alkoxy group can be cited. The specific forms of the above respective groups are as described above. As substituents that the aryl group may have, a methyl group, an isopropyl group, or a methoxy group is preferred.

[0201] As the amino group that may have a substituent represented by Rs, there is no particular limitation, and it can be a primary amino group (-NH2), a secondary amino group (-NR T H), or a tertiary amino group (-NR T 2), any one of them.

[0202] R T represents a substituent that the above amino group may have, and a plurality of R T can be different from each other. As R T , an alkyl group that may have a substituent represented by the above Rs is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred.

[0203] As the silyl group that may have a substituent represented by Rs, a group represented by -Si(R S1 )(R S2 )(R S3 ) can be cited. R S1 , R S2 , and R S3 each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent, and an alkyl group that may have a substituent or an aryl group that may have a substituent is preferred.

[0204] As substituents that each group represented by R S1 , R S2 , and R S3 may have, the groups exemplified in the above substituent W can be cited.

[0205] Moreover, the preferred forms of each group represented by R S1 , R S2 , and R S3 are the same as the preferred forms of an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent represented by Rs, respectively.

[0206] As the halogen atom represented by Rs, a fluorine atom or a chlorine atom is preferred.

[0207] As Rs, preferably represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkynyl group having 2 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group or a halogen atom, more preferably represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, a silyl group which may have a substituent or a halogen atom.

[0208] In terms of more excellent effects of the present invention, in formula (1), D is preferably a group represented by any one of the following formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (3-10), formula (3-11), formula (3-12), formula (3-13), formula (4-10), formula (4-11), formula (5-10) and formula (5-11), more preferably a group represented by any one of formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (3-10), formula (3-11), formula (3-12), formula (3-13), formula (5-10) and formula (5-11).

[0209] Moreover, it is also preferred that D represents a group represented by formula (4-10) or a group represented by formula (4-11). When D represents a group represented by formula (4-10) or a group represented by formula (4-11), the dependence of the quantum efficiency on the electric field strength is more excellent.

[0210] [Chemical formula 2]

[0211]

[0212] In formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (3-10), formula (3-11), formula (3-12), formula (3-13), formula (4-10), formula (4-11), formula (5-10) and formula (5-11), X 21 、X 31 、X41 and X 42 and X 51 and X 52 each independently represents a sulfur atom, an oxygen atom, NR X1 or CR X2 R X3 .

[0213] R X1 to R X3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent,

[0214] R X1 to R X3 are as described above in terms of specific and preferred modes.

[0215] X 21 and X 31 and X 41 and X 42 and X 51 and X 52 are the same as those of X in Formulas (2) to (5) in terms of specific and preferred modes. 21 and X 31 and X 41 and X 42 and X 51 and X 52 are the same.

[0216] In Formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (4-10), (4-11), (5-10) and (5-11), Y 21 and Y 22 and Y 23 and Y 24 and Y 31 and Y 32 and Y 33 and Y 34 and Y 42 and Y 52 each independently represents -CR Y1 = or a nitrogen atom. R Y1 represents a hydrogen atom or a substituent,

[0217] Y 21 and Y 22 and Y 23 and Y 24 and Y 31 and Y 32 and Y 33 and Y 34 and Y42 and Y 52 The specific and preferred ways of [the relevant part] are the same as those of Y in Formulas (2) to (5). 31 Y 22 Y 23 Y 24 Y 31 Y 32 Y 33 Y 34 Y 42 and Y 52 The specific and preferred ways are the same.

[0218] In Formula (2 - 10), preferably at least one of Y 22 to Y 24 represents -CR Y1 =, more preferably at least two represent -CR Y1 =, further preferably Y 22 to Y 24 all represent -CR Y1 =.

[0219] In Formula (2 - 11), preferably at least one of Y 21 Y 23 and Y 24 represents -CR Y1 =, more preferably at least two represent -CR Y1 =, further preferably Y 21 Y 23 and Y 24 all represent -CR Y1 =.

[0220] In Formula (2 - 12), preferably at least one of Y 21 to Y 23 represents -CR Y1 =, more preferably at least two represent -CR Y1 =, further preferably Y 21 to Y 23 all represent -CR Y1 =.

[0221] In Formula (2 - 13), preferably at least one of Y 22 and Y 23 represents -CR Y1 =, more preferably Y 22 and Y 23 all represent -CR Y1 =.

[0222] In Formula (3 - 10), preferably at least one of Y 32 to Y 34 represents -CR Y1=, more preferably at least 2 represent -CR Y1 =, further preferably Y 32 ~Y 34 all represent -CR Y1 =.

[0223] In formula (3-11), preferably Y 31 ~Y 33 at least one of which represents -CR Y1 =, more preferably at least 2 represent -CR Y1 =, further preferably Y 31 ~Y 33 all represent -CR Y1 =.

[0224] In formula (3-12), preferably Y 31 , Y 33 and Y 34 at least one of which represents -CR Y1 =, more preferably at least 2 represent -CR Y1 =, further preferably Y 31 , Y 33 and Y 34 all represent -CR Y1 =.

[0225] In formula (3-13), preferably Y 32 and Y 33 at least one of which represents -CR Y1 =, more preferably Y 32 and Y 33 all represent -CR Y1 =.

[0226] In formula (4-10), Y 42 preferably represents -CR Y1 =.

[0227] In formula (5-10), Y 52 preferably represents -CR Y1 =.

[0228] In formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (3-10), formula (3-11), formula (3-12), formula (3-13), formula (4-10), formula (4-11), formula (5-10) and formula (5-11), Rs represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group or a halogen atom.

[0229] The specific and preferred forms of the above Rs are the same as the specific and preferred forms of Rs in formulas (2) to (5).

[0230] Among them, in formula (1), when D represents a group represented by any one of formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (5-10), and (5-11), in terms of the aspect where the effects of the present invention are more excellent, Rs is preferably a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkynyl group having 2 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group, or a halogen atom.

[0231] Moreover, when D represents a group represented by any one of formulas (4-10) and (4-11), in terms of the aspect where the dependence of the quantum efficiency on the electric field strength is more excellent, Rs is preferably a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, or a group represented by formula (S1) shown below.

[0232] Moreover, the group represented by formula (S1) may be a group represented by formula (S2).

[0233] [Chemical formula 3]

[0234]

[0235] In formula (S1),

[0236] C m represents an aromatic hydrocarbon having 6 to 14 carbon atoms which may have a substituent.

[0237] R m represents a substituent.

[0238] In formula (S1), C m represents an aromatic hydrocarbon having 6 to 14 carbon atoms which may have a substituent. The aromatic hydrocarbon represented by C m may be either monocyclic or polycyclic, and is preferably monocyclic.

[0239] Specific examples of the aromatic hydrocarbon ring and the aromatic heterocyclic ring are as described above.

[0240] By C m The number of substituents that the aromatic hydrocarbon represented by the formula may have (including the R m The number of) is preferably 1 to 5, more preferably 1 to 4, further preferably 1 or 2.

[0241] As C m The substituent that the aromatic hydrocarbon represented by may have includes, for example, the groups exemplified in the above-mentioned substituent W, among which a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a silyl group are preferred, and a methyl group, an isopropyl group, or a methoxy group is more preferred.

[0242] Preferred embodiments of each group (halogen atom, alkyl group, aryl group, alkoxy group and silyl group) exemplified as the above substituent are the same as preferred embodiments of each group exemplified as Rs.

[0243] As C m Among them, an aromatic hydrocarbon having 6 to 10 carbon atoms which may have a substituent is preferred, and a benzene ring which may have a substituent is more preferred.

[0244] In formula (S1), R m represents a substituent.

[0245] As R m The substituent represented by may be, for example, the groups exemplified in the substituent W, among which an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a cyano group or a halogen atom is preferred, and an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent or a halogen atom is more preferred.

[0246] Preferred embodiments of the above-exemplified groups are the same as preferred embodiments of the groups exemplified as Rs.

[0247] In formula (S2),

[0248] C m It represents an aromatic hydrocarbon having 6 to 14 carbon atoms which may have a substituent.

[0249] R m Each independently represents a substituent.

[0250] C in formula (S2) m and R m The preferred embodiment is the same as C in formula (S1) m and Rm is the same as the preferred mode.

[0251] In formula (1), R 1 and R 2 each independently represent a hydrogen atom or a substituent.

[0252] As the substituent represented by R 1 and R 2 , for example, the groups exemplified in the above-mentioned substituent W can be cited. Among them, in terms of the more excellent effects of the present invention, R 1 and R 2 are preferably hydrogen atoms.

[0253] In formula (1), A 1 and A 2 each independently represent the group represented by the above formula (A-1).

[0254] In formula (A-1), W 1 represents a sulfur atom, an oxygen atom, =NR W or =CR W3 R W4 .

[0255] R W2 represents a hydrogen atom or a substituent. R W3 and R W4 each independently represent a cyano group, -SO2R W5 , -COOR W6 or -COR W7 .

[0256] As W 1 , in terms of the more excellent effects of the present invention, it is preferably an oxygen atom or a sulfur atom.

[0257] As the substituent represented by R W2 , for example, the substituents exemplified in the above-mentioned substituent W can be cited.

[0258] And, R W5 ~R W7 each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent or an aliphatic heterocyclic group which may have a substituent.

[0259] As the substituents which the groups represented by R W5 ~R W7 may have, for example, the substituents exemplified in the above-mentioned substituent W can be cited.

[0260] The meaning of the above-mentioned aliphatic hydrocarbon group is as described above, among which, an alkyl group is preferred, and a linear alkyl group is more preferred. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 3.

[0261] The meaning of the above-mentioned aromatic ring group is as described above, among which, aryl is preferred, and phenyl is more preferred.

[0262] The meaning of the above-mentioned aliphatic heterocyclic group is as described above.

[0263] In the above formula (A-1), C 1 represents a ring containing 2 or more carbon atoms and may have substituents.

[0264] The number of carbon atoms of the above ring is preferably 3 to 30, more preferably 3 to 20, and further preferably 3 to 10. In addition, the number of carbon atoms is the number including the 2 carbon atoms explicitly shown in the formula.

[0265] The above ring can be either aromatic or non-aromatic.

[0266] The above ring can be either a monocyclic ring or a polycyclic ring, preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least 1 of the 5-membered ring and the 6-membered ring. The number of rings forming the above fused ring is preferably 1 to 4, more preferably 1 to 3.

[0267] The above ring can have heteroatoms. As the above heteroatoms, for example, nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom, and boron atom can be mentioned, and sulfur atom, nitrogen atom, or oxygen atom is preferred.

[0268] The number of heteroatoms of the above ring is preferably 0 to 10, more preferably 0 to 5.

[0269] Among the carbon atoms constituting the ring represented by the above C 1 except for the carbon atom at the bonding position marked with * in formula (A-1) and the carbon atom bonded to W 1 can be substituted by carbonyl carbon (>C=O) or thiocarbonyl carbon (>C=S).

[0270] As the substituents that the above ring can have, for example, the groups exemplified in the above substituent W can be mentioned, preferably a halogen atom, an alkyl group, an aromatic ring group, or a silyl group, and more preferably a halogen atom or an alkyl group.

[0271] The above alkyl group can be any of linear, branched, and cyclic, and linear is preferred.

[0272] The number of carbon atoms of the above alkyl group is preferably 1 to 10, more preferably 1 to 3.

[0273] In the above formula (A-1), as the ring represented by the above C 1 it is preferably a ring used as an acidic nucleus (for example, the acidic nucleus in merocyanine, etc.), and the following nuclei can be mentioned, for example.

[0274] (a) 1,3-dicarbonyl nucleus: For example, 1,3-indanedione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione, etc.

[0275] (b) Pyrazolone 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, etc.

[0276] (c) Isoxazolone nucleus: For example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc.

[0277] (d) Hydroxyindole nucleus: For example, 1-alkyl-2,3-dihydro-2-hydroxyindole, etc.

[0278] (e) 2,4,6-trioxohexahydropyrimidine nucleus: For example, barbituric acid, 2-thiobarbituric acid and their derivatives, etc. As the above derivatives, for example, 1-alkyl bodies such as 1-methyl, 1-ethyl, etc., 1,3-dialkyl bodies such as 1,3-dimethyl, 1,3-diethyl, 1,3-dibutyl, etc., 1,3-diaryl bodies such as 1,3-diphenyl, 1,3-bis(p-chlorophenyl), 1,3-bis(p-ethoxycarbonylphenyl), etc., 1-alkyl-1-aryl bodies such as 1-ethyl-3-phenyl, etc., and 1,3-diheteroaryl bodies such as 1,3-bis(2-pyridyl), etc.

[0279] (f) 2-thio-2,4-thiazolidinedione nucleus: For example, rhodanine and its derivatives, etc. As the above derivatives, for example, 3-alkyl rhodanines such as 3-methyl rhodanine, 3-ethyl rhodanine, 3-allyl rhodanine, etc., 3-aryl rhodanines such as 3-phenyl rhodanine, etc., and 3-heteroaryl rhodanines such as 3-(2-pyridyl) rhodanine, etc.

[0280] (g) 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazolidinedione nucleus): For example, 3-ethyl-2-thio-2,4-oxazolidinedione, etc.

[0281] (h) Thianaphthenone nucleus: For example, 3(2H)-thianaphthenone-1,1-dioxide, etc.

[0282] (i) 2-thio-2,5-thiazolidinedione nucleus: For example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.

[0283] (j) 2,4-thiazolidinedione nucleus: For example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc.

[0284] (k) Thiazolin-4-one nucleus: For example, 4-thiazolinone, 2-ethyl-4-thiazolinone, etc.

[0285] (l) 2,4-Imidazolidinedione (hydantoin) nucleus: For example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.

[0286] (m) 2-Thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: For example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, etc.

[0287] (n) Imidazolin-5-one nucleus: For example, 2-propylthio-2-imidazolin-5-one, etc.

[0288] (o) 3,5-Pyrazolidinedione nucleus: For example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, etc.

[0289] (p) Benzothiophen-3(2H)-one nucleus: For example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, dioxobenzothiophen-3(2H)-one, etc.

[0290] (q) Indanone nucleus: For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone, etc.

[0291] (r) Benzofuran-3-(2H)-one nucleus: For example, benzofuran-3-(2H)-one, etc.

[0292] (s) 2,2-Dihydrophenalene-1,3-dione nucleus, etc.

[0293] In terms of the aspect where the effects of the present invention are more excellent, the group represented by the above formula (A-1) is preferably the group represented by formula (A-2).

[0294] [Chemical formula 4]

[0295]

[0296] In formula (A-2), * represents the bonding position,

[0297] W 2 and W 3 each independently represents an oxygen atom or a sulfur atom.

[0298] W 2 and W 3 Preferably both represent oxygen atoms.

[0299] Further, in formula (A-2), C 2 represents a ring having 3 or more carbon atoms and may have substituents.

[0300] The above-mentioned C 2 contains 3 carbon atoms which are the 3 carbon atoms specified in formula (A-2).

[0301] The number of carbon atoms in the above-mentioned ring is preferably 3 to 30, more preferably 3 to 20, and still more preferably 3 to 10. The number of carbon atoms in the above-mentioned ring includes the number of 3 carbon atoms specified in the formula.

[0302] The above-mentioned ring can be either an aromatic ring or a non-aromatic ring.

[0303] The above-mentioned ring can be either a monocyclic ring or a polycyclic ring, preferably a 5-membered ring, a 6-membered ring or a fused ring containing at least 1 of a 5-membered ring and a 6-membered ring. When the above-mentioned ring is a polycyclic ring, the number of rings contained is preferably 2 to 6, more preferably 2 or 3.

[0304] The above-mentioned ring can have heteroatoms. Examples of the above-mentioned heteroatoms 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, preferably a sulfur atom, a nitrogen atom or an oxygen atom.

[0305] The number of heteroatoms in the above-mentioned ring is preferably 0 to 10, more preferably 0 to 5.

[0306] Among the carbon atoms constituting the ring represented by the above-mentioned C 2 the carbon atom at the bonding position marked with * in formula (A-2) and the carbon atoms other than the carbon atoms bonded to W 2 and W 3 can be substituted by a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S).

[0307] The preferred mode of the substituents that the above-mentioned ring can have is the same as the substituents that the above-mentioned ring C 1 can have.

[0308] Further, the group represented by the above formula (A-2) is preferably the group represented by formula (C-1) or the group represented by formula (C-2).

[0309] [Chemical formula 5]

[0310]

[0311] In formula (C-1), X c1 and X c2 each independently represents a sulfur atom or an oxygen atom.

[0312] Preferably, the above-mentioned X c1 and Xc2 At least one of them is an oxygen atom, and more preferably X c1 and X c2 are both oxygen atoms.

[0313] In formula (C-1), C 3 represents an aromatic ring which may have substituents.

[0314] The number of carbon atoms of the above aromatic ring is preferably 4 to 30, more preferably 5 to 12, and further preferably 6 to 8. In addition, the number of carbon atoms is the number including the 2 carbon atoms explicitly shown in the formula.

[0315] The above aromatic ring may be either a monocyclic or a polycyclic ring.

[0316] Moreover, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but preferably an aromatic hydrocarbon ring.

[0317] As the aromatic ring represented by the above C 3 the rings exemplified in the description of the above aromatic ring can be cited.

[0318] Among them, as the aromatic ring represented by C 3 a benzene ring, a naphthalene ring, an anthracene ring or a pyrene ring is preferred, and a benzene ring is more preferred.

[0319] As the substituents that the above aromatic ring may have, for example, the groups exemplified in the above substituent W can be cited.

[0320] In the above formula (C-2), X c3 to X c5 represent a sulfur atom or an oxygen atom.

[0321] Preferably, X c3 and X c4 are both oxygen atoms, and more preferably X c3 , X c4 and X c5 are both oxygen atoms.

[0322] Moreover, R c1 and R c2 each independently represent a hydrogen atom or a substituent. As the substituents represented by R c1 and R c2 , for example, the groups exemplified in the above substituent W can be cited, among which an alkyl group or a phenyl group is preferred, and an alkyl group is more preferred.

[0323] The above phenyl group may also have substituents, for example, the groups exemplified in the above substituent W can be cited.

[0324] The molecular weight of the specific compound is preferably 400 to 1,200, more preferably 400 to 1,000, and further preferably 500 to 800.

[0325] It is speculated that, in the case of the above molecular weight, the sublimation temperature of a specific compound is low, and the quantum efficiency is excellent even when the photoelectric conversion film is formed at high speed.

[0326] In terms of the stability when used as a p-type organic semiconductor and the matching of the energy levels with an n-type organic semiconductor, the ionization potential of the specific compound in a single film is preferably -5.0 to -6.0 eV.

[0327] The maximum absorption wavelength of the specific compound is preferably in the range of 400 to 600 nm, more preferably in the range of 400 to 500 nm.

[0328] The above maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) at a concentration that adjusts the absorption spectrum of the specific compound to an absorbance of about 0.5 to 1.0. However, when the specific compound is not soluble in chloroform, the value measured using the specific compound in a film state obtained by vapor-depositing the specific compound is used as the maximum absorption wavelength of the specific compound.

[0329] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging element, a photosensor, or a photovoltaic cell. The specific compound often functions as a pigment in the photoelectric conversion film. In addition, the specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a drug material, and a fluorescent diagnostic agent material.

[0330] Hereinafter, specific examples of D (a group represented by any one of formulas (2) to (5)) in the compound (specific compound) represented by formula (1) are shown, but the present invention is not limited to these.

[0331] [Chemical formula 6]

[0332]

[0333] [Chemical formula 7]

[0334]

[0335] [Chemical formula 8]

[0336]

[0337] [Chemical formula 9]

[0338]

[0339] [Chemical formula 10]

[0340]

[0341] [Chemical Formula 11]

[0342]

[0343] [Chemical Formula 12]

[0344]

[0345] [Chemical Formula 13]

[0346]

[0347] [Chemical Formula 14]

[0348]

[0349] [Chemical Formula 15]

[0350]

[0351] Moreover, the following shows A in the compound (specific compound) represented by formula (1) 1 and A 2 (group represented by formula (A-1)), but the present invention is not limited to these.

[0352] [Chemical Formula 16]

[0353]

[0354] [Chemical Formula 17]

[0355]

[0356] [Chemical Formula 18]

[0357]

[0358] [Chemical Formula 19]

[0359]

[0360] The specific compound can be purified as needed.

[0361] As a purification method of the specific compound, for example, sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, repulping washing, reprecipitation purification, purification using adsorbents such as activated carbon, and recrystallization purification can be mentioned.

[0362] The content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound in terms of a single layer / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and still more preferably 20 to 50% by volume.

[0363] 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 their total amount is within the above range.

[0364] <n-type organic semiconductor>

[0365] The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the above specific compound.

[0366] The n-type organic semiconductor is a compound different from the above specific compound.

[0367] The n-type organic semiconductor is an acceptor-type organic semiconductor material (compound), and refers to an organic compound having a property of easily accepting electrons. That is, the n-type organic semiconductor refers to an organic compound having a large electron affinity when two organic compounds are brought into contact and used. That is, as the acceptor-type organic semiconductor, any organic compound can be used as long as it is an organic compound having electron-accepting properties.

[0368] Examples of the n-type organic semiconductor include fullerenes selected from the group consisting of fullerenes and their derivatives; condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives, etc.); heterocyclic compounds having a 5- to 7-membered ring containing at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, etc.); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride imide derivatives and oxadiazole derivatives; anthraquinodimethane derivatives; diphenyl quinone derivatives; bathocuproine, bathophenanthroline, and their derivatives; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; the compounds described in paragraphs

[0056] to

[0057] of Japanese Patent Laid-Open No. 2006-100767.

[0369] As the n-type organic semiconductor (compound), a fullerene type selected from the group consisting of fullerenes and their derivatives is preferably used.

[0370] Examples of the fullerene include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene C540, and mixed fullerenes.

[0371] Regarding the fullerene derivative, for example, a compound having a substituent attached to the above fullerene can be cited. As the above substituent, an alkyl group, an aryl group, or a heterocyclic group is preferable. As the fullerene derivative, a compound described in Japanese Patent Application Laid-Open No. 2007-123707 is preferably used.

[0372] The n-type organic semiconductor may be an organic dye.

[0373] Examples of the organic dye include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylene 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, acridone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0374] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0375] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less or in the wavelength range of 500 to 600 nm.

[0376] The photoelectric conversion film preferably has a bulk heterojunction structure formed in a state where a specific compound and an n-type organic semiconductor are mixed. The bulk heterojunction structure 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 a bulk heterojunction structure can also be formed by either a wet method or a dry method. In addition, the bulk heterojunction structure is described in detail in paragraphs

[0013] to

[0014] of Japanese Patent Application Laid-Open No. 2005-303266.

[0377] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0378] The n-type organic semiconductor may be used alone or in combination of two or more.

[0379] When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (the film thickness of the n-type organic semiconductor in terms of a single layer / the film thickness of the photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and further preferably 20 to 50% by volume.

[0380] When the n-type organic semiconductor contains fullerenes, the content of the fullerenes relative to the total content of the n-type organic semiconductors (the film thickness of the fullerenes in terms of a single layer / the total film thickness of each n-type organic semiconductor in terms of a single layer × 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. The fullerenes may be used alone or in combination of two or more.

[0381] 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 (the film thickness of the specific compound in terms of a single layer / (the film thickness of the specific compound in terms of a single layer + the film thickness of the n-type organic semiconductor in terms of a single layer) × 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume.

[0382] When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (the film thickness of the specific compound in terms of a single layer / (the film thickness of the specific compound in terms of a single layer + the film thickness of the n-type organic semiconductor in terms of a single layer + the film thickness of the p-type organic semiconductor in terms of a single layer) × 100) is preferably 15 to 75% by volume, more preferably 30 to 75% by volume.

[0383] In addition, the photoelectric conversion film preferably consists essentially of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor included as needed. Substantially, 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.

[0384] <p-type organic semiconductor>

[0385] The photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the above specific compound.

[0386] The p-type organic semiconductor is a compound different from the above specific compound.

[0387] The p-type organic semiconductor is a donor-type organic semiconductor material (compound), and refers to an organic compound having the property of easily donating electrons. That is, the p-type organic semiconductor refers to an organic compound having a small ionization potential when two organic compounds are brought into contact and used.

[0388] The p-type organic semiconductor can be used alone as one kind, or two or more kinds can be used.

[0389] As a p-type organic semiconductor, for example, 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 Japanese Unexamined Patent Application Publication No. 2011-228614, the compounds described in paragraphs

[0052] to

[0063] of Japanese Unexamined Patent Application Publication No. 2011-176259, the compounds described in paragraphs

[0119] to

[0158] of Japanese Unexamined Patent Application Publication No. 2011-225544, the compounds described in paragraphs

[0044] to

[0051] of Japanese Unexamined Patent Application Publication No. 2015-153910, and the compounds described in paragraphs

[0086] to

[0090] of Japanese Unexamined Patent Application Publication No. 2012-094660, etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (e.g., thiophenothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithiophenothiophene derivatives, [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivatives, thiophene[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, the compounds described in paragraphs

[0031] to

[0036] of Japanese Unexamined Patent Application Publication No. 2018-014474, the compounds described in paragraphs

[0043] to

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

[0025] to

[0037] ,

[0099] to

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

[0029] to

[0034] of Japanese Unexamined Patent Application Publication No. 2017-076766, the compounds described in paragraphs

[0015] to

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

[0045] to

[0053] of Japanese Unexamined Patent Application Publication No. 2019-054228, the compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

[0036] of Japanese Unexamined Patent Application Publication No. 2019-080052, the compounds described in paragraphs

[0044] to

[0054] of W02019 / 054125, the compounds described in paragraphs

[0041] to

[0046] of W02019 / 093188), the compounds described in paragraphs

[0034] to

[0037] of Japanese Unexamined Patent Application Publication No. 2019-050398, the compounds described in paragraphs

[0033] to

[0036] of Japanese Unexamined Patent Application Publication No. 2018-206878,The compound described in paragraph

[0038] of Japanese Patent Application Laid-Open No. 2018-190755, the compound described in paragraphs

[0019] to

[0021] of Japanese Patent Application Laid-Open No. 2018-026559, the compound described in paragraphs

[0031] to

[0056] of Japanese Patent Application Laid-Open No. 2018-170487, the compound described in paragraphs

[0036] to

[0041] of Japanese Patent Application Laid-Open No. 2018-078270, the compound described in paragraphs

[0036] to

[0041] of Japanese Patent Application Laid-Open No. 2018-16620 The compounds described in paragraphs

[0055] to

[0082] of Japanese Patent Application No. 0, the compounds described in paragraphs

[0041] to

[0050] of Japanese Patent Application No. 2018-113425, the compounds described in paragraphs

[0044] to

[0048] of Japanese Patent Application No. 2018-085430, the compounds described in paragraphs

[0041] to

[0045] of Japanese Patent Application No. 2018-056546, the compounds described in paragraphs

[0041] to

[0045] of Japanese Patent Application No. 2018-046267, 0042] to

[0049] , compounds described in paragraphs

[0031] to

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

[0036] to

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

[0045] to

[0048] of JP-A-2020-010024, etc.), cyanine compounds, oxonocyanine compounds, polyamine compounds, indole compounds, pyrrole compounds , pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives and fluoranthene derivatives, etc.), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyaryl alkane compounds, pyrazoline compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds and metal complexes having nitrogen-containing heterocyclic compounds as ligands. ,

[0390] In addition, as p-type organic semiconductors, benzoxazole compounds (for example, the compounds described in Figures 3 to 7 of Japanese Patent Publication No. 2022-123944), dicarbazole compounds (for example, the compounds described in Figures 3 to 7 of Japanese Patent Publication No. 2022-122839), Figure 2 5), benzoquinazoline compounds (for example, compounds described in paragraphs

[0053] to

[0056] of Japanese Patent Application Laid-Open No. 2022-120323), azine compounds (for example, compounds described in paragraphs

[0041] to

[0042] of Japanese Patent Application Laid-Open No. 2022-120273), and compounds described in paragraphs

[0054] to

[0056] of Japanese Patent Application Laid-Open No. 2022-115832. Figure 2 - 1Compounds described in [0], indole-fused triphenylene compounds (e.g., compounds described in paragraphs

[0065] to

[0072] of JP-A-2022-108268), indole-fused carbazole compounds (e.g., compounds described in paragraphs

[0052] to

[0073] of JP-A-2023-005703 and paragraph

[0028] of JP-A-2022-100258), tricarbazolylphenyl compounds (e.g., compounds described in paragraphs

[0038] to

[0040] of JP-A-2022-181226), compounds described in paragraphs

[0070] to

[0082] of JP-A-2022-027575, and compounds described in paragraphs

[0051] to

[0064] of JP-A-2021-163968, etc.

[0391] As the p-type organic semiconductor, for example, a compound having an ionization potential lower than that of the n-type organic semiconductor can also be cited. As long as this condition is satisfied, the organic dyes exemplified as the n-type organic semiconductor can be used.

[0392] Compounds that can be used as p-type organic semiconductor compounds are exemplified below.

[0393] [Chemical formula 20]

[0394]

[0395] [Chemical formula 21]

[0396]

[0397] [Chemical formula 22]

[0398]

[0399] [Chemical formula 23]

[0400]

[0401] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0402] The p-type semiconductor material can be used alone or in combination of two or more.

[0403] 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 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.

[0404] The optoelectronic conversion film containing a specific compound is a non-luminescent film and has characteristics different from those of an organic light-emitting diode (OLED). The non-luminescent film refers to a film with 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.

[0405] <Dye

[0406] In addition to the above specific compound, the optoelectronic conversion film may also contain a dye.

[0407] The dye is a compound different from the above specific compound.

[0408] As the dye, an organic dye is preferred.

[0409] As the organic dye, for example, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squaraine dyes, croconium dyes, azomethine dyes, coumarin dyes, arylene 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, acridone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, imidazoquinoxaline dyes described in WO2020 / 013246, WO2022 / 168856, Japanese Patent Laid-Open No. 2023-010305 and Japanese Patent Laid-Open No. 2023-010299, and donor-acceptor-donor type dyes formed by bonding two acidic nuclei to a donor and donor-acceptor-donor type dyes formed by bonding two donors to an acceptor, etc.

[0410] As the organic dye, among them, cyanine dyes, imidazoquinoxaline dyes or donor-acceptor-donor type dyes are preferred, and imidazoquinoxaline dyes or donor-acceptor-donor type dyes are more preferred.

[0411] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and further preferably in the wavelength range of 450 to 650 nm.

[0412] The dye can be used alone as one kind or two or more kinds can be used.

[0413] The content of the pigment in the photoelectric conversion film is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and further preferably 20 to 50% by volume, relative to the total content of the specific compound and the pigment (= (film thickness of the pigment in monolayer conversion / (film thickness of the specific compound in monolayer conversion + film thickness of the pigment in monolayer conversion) × 100)).

[0414] <Film forming method>

[0415] As a film forming method of the above-mentioned photoelectric conversion film, for example, a dry film forming method can be cited.

[0416] As the dry film forming method, for example, physical vapor deposition methods such as evaporation method (especially, vacuum evaporation method), sputtering method, ion plating method, and MBE (Molecular Beam Epitaxy) method, and CVD (Chemical Vapor Deposition) methods such as plasma polymerization can be cited, and the vacuum evaporation method is preferred. When forming the photoelectric conversion film by the vacuum evaporation method, manufacturing conditions such as the degree of vacuum and evaporation temperature can be set according to the conventional method.

[0417] The film thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and further preferably 50 to 500 nm.

[0418] 〔Electrode〕

[0419] The photoelectric conversion element preferably has an electrode.

[0420] The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. As the conductive material, metals, alloys, metal oxides, conductive compounds, and mixtures thereof can be cited.

[0421] Since light enters from the upper electrode 15, it is preferred that the upper electrode 15 is transparent to the light to be detected. As the material constituting the upper electrode 15, for example, conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO: Indium Zinc Oxide); metal thin films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and nanocarbon materials such as carbon nanotubes and graphene can be cited. In terms of high conductivity and transparency, conductive metal oxides are preferred.

[0422] Generally, if the conductive film is made thinner than a certain range, the resistance value often increases sharply. In the solid-state imaging device equipped with the photoelectric conversion element of this embodiment, the sheet resistance can be 100 to 10,000 Ω / square, and the degree of freedom of the film thickness range that can be made thinner is large.

[0423] Moreover, the thinner the film thickness of the upper electrode (transparent conductive film) 15 is, the less the amount of light absorbed, and generally the light transmittance increases. The increase in light transmittance increases the light absorption in the photoelectric conversion film, thereby increasing the photoelectric conversion ability, which is therefore preferable. Considering the suppression of leakage current accompanying thinning, the increase in the resistance value of the thin film, and the increase in transmittance, the thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm.

[0424] The lower electrode 11 may be transparent or, conversely, may be non-transparent to reflect light depending on the application. Examples of the material constituting the lower electrode 11 include conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (for example, titanium nitride (TiN), etc.); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.

[0425] As a method for forming the electrode, it can be appropriately selected according to the electrode material. Specifically, wet methods such as printing methods and coating methods; physical methods such as vacuum evaporation, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD can be cited.

[0426] When the electrode material is ITO, methods such as electron beam method, sputtering method, resistance heating evaporation method, chemical reaction method (sol-gel method, etc.), and coating of a dispersion of indium tin oxide can be cited.

[0427] [Charge blocking film: Electron blocking film, Hole blocking film]

[0428] The photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

[0429] As the above intermediate layer, for example, a charge blocking film can be cited. When the photoelectric conversion element has this film, the characteristics (quantum efficiency, response speed, etc.) of the obtained photoelectric conversion element are more excellent. As the charge blocking film, for example, an electron blocking film and a hole blocking film can be cited.

[0430] [Electron blocking film]

[0431] The electron blocking film is a donor-type organic semiconductor material (compound) and can use the above-mentioned p-type organic semiconductor.

[0432] Moreover, as the electron blocking film, a polymer material can also be used.

[0433] As the polymer material, for example, polymers such as poly(phenylene vinylene), fluorene, carbazole, indole, pyrene, pyrrole, methylpyridine, thiophene, acetylene, and butadiyne and their derivatives can be cited.

[0434] In addition, the electron blocking film can be composed of multiple films.

[0435] The electron blocking film can be composed of an inorganic material. Generally, since the dielectric constant of the inorganic material is larger than that of the organic material, when the inorganic material is used for the electron blocking film, a relatively large voltage is applied to the photoelectric conversion film, and thus the quantum efficiency is high. As the inorganic material that can be an electron blocking film, for example, calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide can be cited.

[0436] 〔Hole blocking film〕

[0437] The hole blocking film is an acceptor-type organic semiconductor material (compound) and can utilize the above-mentioned n-type organic semiconductor.

[0438] In addition, the hole blocking film can be composed of multiple films.

[0439] As a method for manufacturing the charge blocking film, for example, a dry film forming method and a wet film forming method can be cited. As the dry film forming method, for example, an evaporation method and a sputtering method can be cited. The evaporation method can be either a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, and a physical evaporation method such as a vacuum evaporation method is preferred. As the wet film forming method, for example, an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, and an intaglio coating method can be cited, and the inkjet method is preferred in terms of high-precision patterning.

[0440] The film thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and still more preferably 5 to 30 nm, respectively.

[0441] 〔Substrate〕

[0442] The photoelectric conversion element may further have a substrate.

[0443] As the substrate, for example, a semiconductor substrate, a glass substrate, or a plastic substrate can be cited.

[0444] In addition, the position of the substrate is usually such that a conductive film, a photoelectric conversion film, and a transparent conductive film are sequentially stacked on the substrate.

[0445] [Sealing layer]

[0446] The photoelectric conversion element may also have a sealing layer.

[0447] Due to the presence of deterioration factors such as water molecules, the performance of the photoelectric conversion material sometimes deteriorates significantly. Therefore, the entire photoelectric conversion film is coated and sealed with a dense ceramic such as a metal oxide, a metal nitride, or a metal oxynitride that does not allow water molecules to penetrate, or diamond-like carbon (DLC), thereby preventing the above-mentioned deterioration.

[0448] In addition, as the sealing layer, for example, the sealing layer described in paragraphs

[0210] to

[0215] of Japanese Patent Application Laid-Open No. 2011-082508 can be cited, and these contents are incorporated into this specification.

[0449] [Manufacturing method of photoelectric conversion element]

[0450] As the manufacturing method of the photoelectric conversion element, a known manufacturing method can be cited.

[0451] Specifically, for example, a manufacturing method of a photoelectric conversion element can be cited, which includes: 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.

[0452] The manufacturing method of the photoelectric conversion element may have other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer) other than the above.

[0453] The methods for forming each layer are as described above.

[0454] [Imaging element]

[0455] As the use of the photoelectric conversion element, for example, an imaging element can be cited.

[0456] An imaging element is an element that converts the optical information of an image into an electrical signal. Usually, it means that a plurality of photoelectric conversion elements are arranged in a matrix on the same plane, and in each photoelectric conversion element (pixel), the optical signal can be converted into an electrical signal and the electrical signal can be sequentially output to the outside of the imaging element for each pixel. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0457] The manufacturing method of the imaging element is not particularly limited, and a method including the above-described steps of manufacturing the photoelectric conversion element can be cited.

[0458] [Optical sensor]

[0459] As other uses of the photoelectric conversion element, for example, a photovoltaic cell and an optical sensor can be cited. The photoelectric conversion element of the present invention is preferably used as an optical sensor. As the optical sensor, the above-described photoelectric conversion element can be used alone, or it can be used as a line sensor in which the above-described photoelectric conversion elements are arranged linearly or a two-dimensional sensor arranged on a plane.

[0460] [Compound]

[0461] The present invention also includes an invention of a compound. The compound of the present invention is the above-described specific compound.

[0462] [Examples]

[0463] Hereinafter, the present invention will be described in more detail based on examples.

[0464] The materials, amounts used, ratios, treatment contents, treatment steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0465] [Materials used in the production of the photoelectric conversion element]

[0466] The following shows each material used in the production of the photoelectric conversion element.

[0467] [Synthesis of Compound B-8 (Synthesis Example 1 of Specific Compound)]

[0468] Compound B-8, which is a specific compound in the present invention, was synthesized according to the following scheme.

[0469] [Chemical formula 24]

[0470]

[0471] [Synthesis of Intermediate B-8A]

[0472] Intermediate B-8A was synthesized using thiophene-2-carboxaldehyde and dimethyl succinate as starting materials according to the method described in the literature of Asian J. Chem. 2004, 16, 823.

[0473] [Synthesis of Intermediate B-8B]

[0474] To a 500 mL three-necked flask, intermediate B-8A (23.5 g) and dehydrated methanol (200 mL) were added. While stirring under a nitrogen atmosphere at room temperature, potassium carbonate (26.1 g) was added, and then the mixture was heated under reflux for 30 minutes.

[0475] To the obtained reaction solution, 300 mL of water, 24.6 g of ammonium chloride and 200 mL of ethyl acetate were added, and liquid separation and extraction were carried out to recover the organic phase. The obtained organic phase was dried with magnesium sulfate, and then the solvent was removed. The obtained crude product was crystallized with ethyl acetate / hexane to obtain 17.5 g of intermediate B-8B (yield 90%).

[0476] <Synthesis of intermediate B-8C>

[0477] To a 1 L three-necked flask, intermediate B-8B (15.5 g) and dehydrated dichloromethane (300 mL) were added. While stirring under a nitrogen atmosphere at 0 °C, dehydrated pyridine (7.2 mL) and trifluoromethanesulfonic anhydride (14.0 mL) were added, and the mixture was stirred for 30 minutes.

[0478] To the obtained reaction solution, 300 mL of saturated brine was added, and liquid separation and extraction were carried out to recover the organic phase. The obtained organic phase was dried with magnesium sulfate, and then the solvent was removed. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 85 / 15) to obtain 25.0 g of intermediate B-8C (yield 99%).

[0479] <Synthesis of intermediate B-8D>

[0480] To a 1 L three-necked flask, intermediate B-8C (12.3 g), 2,6-dimethylphenylboronic acid (16.3 g), cesium carbonate (35.3 g), methoxycyclopentane (CPME) (246 mL) and water (24.6 mL) were added. While stirring under a nitrogen atmosphere at room temperature, SPhos Pd G3 (1.45 g) was added, and the mixture was heated under reflux for 1.5 hours.

[0481] The obtained reaction solution was filtered through diatomaceous earth, and the obtained filtrate was subjected to liquid separation and extraction. The obtained organic phase was dried with sodium sulfate, and then the solvent was removed. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 85 / 15) to obtain 8.8 g of intermediate B-8D (yield 82%).

[0482] <Synthesis of intermediate B-8E>

[0483] In a nitrogen atmosphere, to a 500 mL three-necked flask were added intermediate B-8D (8.8 g) and dehydrated tetrahydrofuran (180 mL), and while stirring at 0 °C, a tetrahydrofuran solution of lithium aluminum hydride (1 mol / L, 30 mL) was added dropwise. After that, the mixture was stirred at 0 °C for 15 minutes.

[0484] To the obtained reaction solution were added dropwise water (180 mL), 15 wt% aqueous sodium hydroxide solution (1.14 mL), and water (3.42 mL) in sequence, and the precipitated solid was removed by filtration. After drying the obtained solution with magnesium sulfate, the solvent was removed by distillation to obtain 7.6 g of intermediate B-8E (yield 95%).

[0485] <Synthesis of Intermediate B-8F>

[0486] To a 500 mL three-necked flask were added intermediate B-8E (7.6 g) and dichloromethane (152 mL), and while stirring at room temperature, Dess-Martin reagent (12.0 g) was added. After that, the mixture was stirred at room temperature for 2 hours.

[0487] To the obtained reaction solution was added an aqueous solution prepared by dissolving 8.32 g of sodium thiosulfate in 180 mL of water. After liquid separation, the obtained organic phase was dried with sodium sulfate, and then the solvent was removed. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 80 / 20) to obtain 6.6 g of intermediate B-8F (yield 87%).

[0488] <Synthesis of Intermediate B-8G>

[0489] To a 300 mL three-necked flask were added intermediate B-8F (6.6 g), toluene (100 mL), and ethylene glycol (12.4 mL), and while stirring at room temperature, 0.94 g of p-toluenesulfonic acid monohydrate was added. After that, the mixture was heated to reflux for 2 hours.

[0490] To the obtained reaction solution were added 2.07 mL of triethylamine, 100 mL of water, and 50 mL of ethyl acetate, and the organic phase was recovered by liquid separation. To the obtained organic phase was added saturated brine and stirred, and then the organic phase was recovered by liquid separation. The obtained organic phase was dried with sodium sulfate, and then the solvent was removed. The obtained crude product was purified by amino silica gel column chromatography (eluent: hexane / ethyl acetate = 90 / 10) to obtain 6.0 g of intermediate B-8G (yield 78%).

[0491] <Synthesis of Intermediate B-8H>

[0492] Under a nitrogen atmosphere, intermediate B-8G (1.0 g) and dehydrated tetrahydrofuran (20 mL) were added to a 100 mL three-necked flask. While stirring at 0 °C, a solution of lithium diisopropylamide in tetrahydrofuran (1.07 mol / L, 3.4 mL) was added dropwise. After that, the mixture was stirred at 0 °C for 20 minutes. 0.37 mL of dehydrated N,N-dimethylformamide was added to the reaction solution, and the temperature was raised to room temperature and stirred for 1.5 hours. After adding 20 mL of saturated brine and 20 mL of ethyl acetate and stirring, the organic phase obtained by liquid separation was dried over sodium sulfate, and then the solvent was removed.

[0493] The obtained concentrate was dissolved in 16.5 mL of tetrahydrofuran. While stirring at room temperature, 3.3 mL of 30% by mass hydrochloric acid was added. After that, the mixture was stirred at room temperature for 15 minutes. 5 mL of triethylamine, 10 mL of water and 10 mL of ethyl acetate were added to the reaction solution. The organic phase was recovered by liquid separation and dried over sodium sulfate, and then the solvent was removed.

[0494] The obtained crude product was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 90 / 10) to obtain 0.23 g of intermediate B-8H (yield 27%).

[0495] <Synthesis of Compound B-8>

[0496] Intermediate B-8H (200 mg), 1,3-indanedione (263 mg) and acetic acid (20 mL) were added to a 50 mL eggplant-shaped flask. While stirring at room temperature, piperidine (23 μL) was added, and the reaction was carried out at 100 °C for 4 hours.

[0497] After the reaction was completed, the precipitated solid was recovered by filtration, and the obtained crude product was recrystallized from chloroform and methanol. The obtained solid was purified by sublimation to obtain 184 mg of compound B-8 (yield 49%).

[0498] The following shows the 1 1H-NMR (Nuclear Magnetic Resonance) data of the obtained compound B-8.

[0499] 1 1H-NMR (CD2Cl2): δ = 9.26 (1H, s), 8.22 (1H, d), 8.10 - 8.00 (5H, m), 7.99 (1H, d), 7.92 - 7.86 (4H, m), 7.76 (1H, s), 7.36 (1H, dd), 7.28 (2H, d), 2.07 (6H, s)

[0500] 〔Synthesis of Compound B-47 (Synthesis Example 2 of Specific Compound)〕

[0501] Compound B-47, a specific compound in the present invention, was synthesized according to the following scheme.

[0502] [Chemical formula 25]

[0503]

[0504] <Synthesis of Intermediate B-47A>

[0505] To a 1 L three-necked flask were added 3,6-dibromothieno[3,2-b]thiophene (10.0 g), 2,6-dimethylphenylboronic acid (15.2 g), potassium carbonate (29.0 g), tetrahydrofuran (250 mL), and water (76 mL). After stirring at room temperature under a nitrogen atmosphere, SPhos Pd G3 (1.87 g) was added, and then the reaction solution was heated to reflux overnight.

[0506] The obtained reaction solution was allowed to stand, and after removing the aqueous phase by liquid separation, 200 mL of saturated brine was added and stirred. Then, the organic phase was recovered by liquid separation. To this organic phase, 200 mL of dichloromethane was added, and after drying with magnesium sulfate, the solvent was removed. The obtained crude product was dispersed and washed with dichloromethane to obtain 7.5 g of Intermediate B-47A (yield 64%).

[0507] <Synthesis of Intermediate B-47B>

[0508] To a 1 L three-necked flask were added Intermediate B-47A (8.0 g) and N,N-dimethylformamide (400 mL). While stirring at room temperature, N-bromosuccinimide (12.3 g) was added, and the mixture was stirred at 40 °C for 4 hours.

[0509] The substance precipitated from the obtained reaction solution was recovered by filtration to obtain a crude product. The crude product was completely dissolved in heated chloroform and then ice-cooled to precipitate crystals. The precipitated crystals were recovered by filtration to obtain 6.2 g of Intermediate B-47B (yield 53%).

[0510] <Synthesis of Intermediate B-47C>

[0511] In a nitrogen atmosphere, intermediate B-47B (1.0 g) and dehydrated tetrahydrofuran (40 mL) were added to a 100 mL three-necked flask. While stirring at -65 °C, a n-hexane solution of n-butyllithium (1.6 mol / L, 3.7 mL) was added dropwise. After that, the mixture was stirred at -65 °C for 30 minutes. 0.69 mL of dehydrated N,N-dimethylformamide was added to the reaction solution, and the temperature was raised to room temperature and stirred for 1.5 hours. 10 mL of saturated ammonium chloride aqueous solution, 15 mL of 1N dilute hydrochloric acid, and 20 mL of ethyl acetate were added and stirred. Then, the organic phase was recovered and saturated brine was added.

[0512] The organic phase was recovered by liquid separation and dried over sodium sulfate, and then the solvent was removed. The obtained crude product was crystallized with dichloromethane / ethyl acetate / methanol to obtain 0.35 g of intermediate B-47C (yield 43%).

[0513] <Synthesis of Compound B-47>

[0514] Intermediate B-47C (250 mg), 1,3-dimethylbarbituric acid (251 mg), and acetic acid (25 mL) were added to a 100 mL eggplant-shaped flask. While stirring at room temperature, piperidine (24 μL) was added, and the mixture was reacted at 100 °C for 1.5 hours.

[0515] After the reaction was completed, the precipitated solid was recovered by filtration, and the crude product was recrystallized from dichloromethane and methanol. The obtained solid was purified by sublimation to obtain 218 mg of compound B-47 (yield 59%).

[0516] The following shows the 1 1H-NMR data of the obtained compound B-47.

[0517] 1 1H-NMR (CDCl3): δ = 8.36 (2H, s), 7.38 (2H, dd), 7.25 (4H, d), 3.38 (6H, s), 3.32 (6H, s), 2.05 (12H, s)

[0518] Regarding specific compounds and comparative compounds used in the photoelectric conversion film other than the above compound B-8 and compound B-47, synthesis was carried out with reference to the above [Synthesis of Compound B-8] and [Synthesis of Compound B-47].

[0519] The following shows each material used in the photoelectric conversion element. In addition, compounds B-1 to B-73 correspond to the specific compounds used in the examples, and compounds C1 to C3 correspond to the comparative compounds used in the comparative examples.

[0520] 〔Specific Compounds and Comparative Compounds〕

[0521] [Chemical Formula 26]

[0522]

[0523] [Chemical Formula 27]

[0524]

[0525] [Chemical Formula 28]

[0526]

[0527] [Chemical Formula 29]

[0528]

[0529] [Chemical Formula 30]

[0530]

[0531] [Chemical Formula 31]

[0532]

[0533] [n-type organic semiconductor]

[0534] ·C60: Fullerene (C 60 )

[0535] [p-type organic semiconductor]

[0536] [Chemical Formula 32]

[0537]

[0538] [Evaluation]

[0539] Photovoltaic conversion elements were fabricated using the above-described respective materials, and the following evaluations were carried out.

[0540] [Fabrication of Photovoltaic Conversion Element]

[0541] Photovoltaic conversion elements were fabricated using the various components shown above Figure 2 in the manner described. Among them, the photovoltaic conversion element is composed of a lower electrode 11, an electron blocking film 16A, a photovoltaic conversion film 12, a hole blocking film 16B, and an upper electrode 15.

[0542] Specifically, an amorphous ITO film was formed on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and an electron blocking material (EB-1 or EB-3) shown in Tables 1 to 3 was further formed on the lower electrode 11 by vacuum heating evaporation to form the electron blocking film 16A (thickness: 30 nm).

[0543] Next, for the glass substrate, at room temperature, each specific compound or each comparative compound shown in Tables 1 to 3, the n-type organic semiconductor (fullerene (C 60 )) and the p-type organic semiconductor were co-evaporated on the electron blocking film 16A in a single-layer equivalent of 80 nm to form a film. Thus, a photoelectric conversion film 12 having a bulk heterojunction structure of 240 nm was formed. At this time, the film formation rate of the photoelectric conversion film 12 was set to

[0544] Furthermore, a hole blocking film 16B (thickness: 10 nm) was formed by evaporating a compound (EB-2) on the photoelectric conversion film 12. An upper electrode 15 (transparent conductive film) (thickness: 10 nm) was formed by depositing amorphous ITO on the hole blocking film 16B by sputtering. After forming a SiO film as a sealing layer on the upper electrode 15 by vacuum evaporation, an aluminum oxide (Al2O3) layer was formed thereon by ALCVD (Atomic Layer Chemical Vapor Deposition), and the obtained laminate was heated at 150 °C for 30 minutes in a glove box to obtain the photoelectric conversion elements of each example and each comparative example.

[0545] [Chemical formula 33]

[0546]

[0547] <Dark current>

[0548] Regarding each of the obtained photoelectric conversion elements, the dark current was measured by the following method.

[0549] A voltage was applied to the lower electrode and the upper electrode of each photoelectric conversion element so that the electric field strength reached 2.5×10 5 V / cm, and the current value in the dark (dark current) was measured. As a result, it was confirmed that in any photoelectric conversion element, the dark current was 50 nA / cm 2 Below, and shows a sufficiently low dark current.

[0550] <Quantum efficiency>

[0551] Regarding each of the obtained photoelectric conversion elements, the quantum efficiency was measured by the following method.

[0552] A voltage was applied to each photoelectric conversion element so that the electric field strength reached 2.0×10 5After reaching 2.0×10^4 V / cm, light was irradiated from the upper electrode (transparent conductive film) side, and the quantum efficiency (photovoltaic conversion efficiency) at a wavelength of 460 nm was evaluated, and the quantum efficiency was calculated according to formula (S1).

[0553] Formula (S1): Quantum efficiency (relative ratio) = (Quantum efficiency of each example or each comparative example at a wavelength of 460 nm) / (Quantum efficiency of Examples 1 - 47 at a wavelength of 460 nm)

[0554] (Evaluation criteria)

[0555] A: The quantum efficiency is 1.6 or more

[0556] B: The quantum efficiency is 1.2 or more and less than 1.6

[0557] C: The quantum efficiency is 0.8 or more and less than 1.2

[0558] D: The quantum efficiency is 0.4 or more and less than 0.8

[0559] E: The quantum efficiency is less than 0.4

[0560] <Dependence of quantum efficiency on electric field strength>

[0561] Regarding each photovoltaic conversion element, the dependence of the quantum efficiency on the electric field strength was evaluated by the following method.

[0562] In the above evaluation of [Quantum efficiency], the voltage applied to each photovoltaic conversion element was changed to 7.5×10^4 4 V / cm, and except for this, the quantum efficiency (photovoltaic conversion efficiency) at 7.5×10^4 4 V / cm was measured in the same procedure.

[0563] The dependence of the quantum efficiency on the electric field strength was calculated according to formula (S10), and the dependence of the quantum efficiency on the electric field strength was evaluated according to the following criteria. In addition, in formula (S10), the numerator and denominator are values measured for the same photovoltaic conversion element. The dependence of the quantum efficiency on the electric field strength is preferably evaluated as C or more.

[0564] Formula (S10): Dependence of quantum efficiency on electric field strength = (Quantum efficiency of each photovoltaic conversion element at an applied voltage of 7.5×10^4 4 V / cm) / (Quantum efficiency of each photovoltaic conversion element at an applied voltage of 2.0×10^4 5 V / cm)

[0565] A: The dependence of the quantum efficiency on the electric field strength is 0.9 or more

[0566] B: The dependence of the quantum efficiency on the electric field strength is 0.8 or more and less than 0.9

[0567] C: The dependence of the quantum efficiency on the electric field strength is 0.7 or more and less than 0.8

[0568] D: The dependence of the quantum efficiency on the electric field strength is less than 0.7

[0569] <Response speed>

[0570] For each of the obtained photoelectric conversion elements, the response speed was evaluated by the following method.

[0571] A voltage was applied to the photoelectric conversion element to make the intensity reach 2.0×10 5 V / cm. Then, an LED (light emitting diode) was instantaneously lit and light was irradiated from the upper electrode (transparent conductive film) side. The photocurrent at a wavelength of 460 nm at this time was measured with an oscilloscope, and the rise time from 0% signal intensity to 97% signal intensity was measured, and the relative response speed was evaluated according to Equation (S2).

[0572] Equation (S2): Relative response speed = (rise time at a wavelength of 460 nm for each example or each comparative example) / (rise time at a wavelength of 460 nm for Examples 1-47)

[0573] (Evaluation criteria)

[0574] A: The relative response speed is less than 0.5

[0575] B: The relative response speed is 0.5 or more and less than 1.0

[0576] C: The relative response speed is 1.0 or more and less than 1.5

[0577] D: The relative response speed is 1.5 or more and less than 2.0

[0578] E: The relative response speed is 2.0 or more

[0579] <Dependence of response speed on electric field strength>

[0580] For each of the obtained photoelectric conversion elements, the dependence of the response speed on the electric field strength was evaluated by the following method.

[0581] In the evaluation of the response speed, the voltage applied to each photoelectric conversion element was changed to 7.5×10 4 V / cm, and except for this, the response speed at 7.5×10 4 V / cm was measured in the same procedure.

[0582] The dependence of the response speed on the electric field strength was obtained according to Equation (S3) and evaluated.

[0583] Formula (S3): Dependence of response speed on electric field strength = (Rise time at 7.5×10 4 V / cm at a wavelength of 460 nm for each example or comparative example) / (Rise time at 2.0×10 5 V / cm at a wavelength of 460 nm for each example or comparative example)

[0584] In addition, in Formula (S3), the photoelectric conversion elements in the numerator and denominator are the same.

[0585] For example, regarding Example 1-1, compare the rise time at 7.5×10 4 V / cm at a wavelength of 460 nm for the photoelectric conversion efficiency of Example 1-1 with the rise time at 2.0×10 5 V / cm at a wavelength of 460 nm for the photoelectric conversion efficiency of Example 1-1.

[0586] (Evaluation criteria)

[0587] A: Dependence of response speed on electric field strength is less than 2.0

[0588] B: Dependence of response speed on electric field strength is 2.0 or more and less than 3.0

[0589] C: Dependence of response speed on electric field strength is 3.0 or more and less than 4.0

[0590] D: Dependence of response speed on electric field strength is 4.0 or more and less than 5.0

[0591] E: Dependence of response speed on electric field strength is 5.0 or more

[0592] <Manufacturing applicability (evaporation heat resistance)>

[0593] The film formation speed of the photoelectric conversion film 12 was set to 3.0 Å / second, and except for this, the photoelectric conversion element (B) of each example or comparative example was fabricated in the same steps as the photoelectric conversion element (A). Using the obtained photoelectric conversion element (B), evaluation was carried out in the same method as the above <Quantum efficiency>.

[0594] Compare the quantum efficiency of the photoelectric conversion element (A) and the photoelectric conversion element (B) having the same structure of the same example or comparative example, calculate the relative ratio B / A of "Quantum efficiency of the photoelectric conversion element (B) / Quantum efficiency of the photoelectric conversion element (A)", and evaluate the manufacturing applicability of each photoelectric conversion element by comparing the obtained value with the following criteria. A compound with excellent evaluation results indicates that it is a material whose performance is not easily degraded when forming a film at high speed, indicating excellent manufacturing applicability.

[0595] (Evaluation Criteria)

[0596] A: The relative ratio B / A is 0.90 or more

[0597] B: The relative ratio B / A is 0.85 or more and less than 0.90

[0598] C: The relative ratio B / A is 0.80 or more and less than 0.85

[0599] D: The relative ratio B / A is 0.75 or more and less than 0.80

[0600] E: The relative ratio B / A is less than 0.75

[0601] The above evaluation results are shown in Tables 1 to 3.

[0602] Each expression in Tables 1 to 3 represents the following content.

[0603] The "D" column indicates which one of the groups represented by Formulas (2) to (5) the D in the compound corresponds to.

[0604] The "Formulas (2-10) to (5-11)" column indicates which one of the groups represented by Formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (4-10), (4-11), (5-10), and (5-11) the D in Formula (1) corresponds to. When D does not correspond to any of the formulas, it is marked as "B".

[0605] In the "W 1 = O or S" column, the case where W 1 in Formula (A-1) is an oxygen atom or a sulfur atom is marked as "A", and the cases other than the above are marked as "B".

[0606] In the "Formula (A-1) = Formula (A-2)" column, the case where the group represented by the above Formula (A-1) is the group represented by the above Formula (A-2) is marked as "A", and the cases other than the above are marked as "B".

[0607] In the "Formula (A-1) = Formula (C-1) or Formula (C-2)" column, the case where the group represented by Formula (A-1) in Formula (1) is the group represented by the above Formula (C-1) or the above Formula (C-2) is marked as "A", and the cases other than the above are marked as "B".

[0608] In the "X = O" column, the case where both X c1 and X c2 are oxygen atoms in Formula (C-1) or the case where both X c3 and X c4The case where all are oxygen atoms is labeled as "A", and cases other than the above are labeled as "B".

[0609] In the 'Rs' column, the case where Rs in formula (1) represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, or a halogen atom is labeled as "A", and cases other than the above are labeled as "B".

[0610] [Table 1]

[0611]

[0612] [Table 2]

[0613]

[0614] [Table 3]

[0615]

[0616] From the results in the table, it was confirmed that the quantum efficiency of the photoelectric conversion element of the embodiment of the present invention is excellent. Also, it was confirmed that the dependence of the quantum efficiency of the photoelectric conversion element of the present invention on the electric field strength, the response speed, the dependence of the response speed on the electric field strength, and the manufacturing applicability are also excellent.

[0617] On the other hand, the quantum efficiency of the photoelectric conversion element of the comparative example using a comparative compound not corresponding to the specific compound is insufficient.

[0618] Also, from the comparison of Example 1-1 to Example 1-22 (D is a group represented by formula (2)), Example 1-23 to Example 1-36 (D is a group represented by formula (3)), Example 1-37 to Example 1-49 (D is a group represented by formula (4)), and Example 1-50 to Example 1-63 (D is a group represented by formula (5)), etc., it was confirmed that when it is a group represented by formula (2), formula (3), or formula (5), the quantum efficiency is more excellent, and when it is a group represented by formula (2), the quantum efficiency is further excellent.

[0619] It was confirmed that when D represents a group represented by any one of Formula (2-10), Formula (2-11), Formula (2-12), Formula (2-13), Formula (3-10), Formula (3-11), Formula (3-12), Formula (3-13), Formula (4-10), and Formula (5-10), the response speed is more excellent. Further, it was confirmed that when D represents a group represented by any one of Formula (2-11), Formula (2-12), Formula (3-11), and Formula (3-13), the response speed is further excellent.

[0620] From the comparison between Examples 1-22 and 1-36 and other examples etc., it was confirmed that in a specific compound, when D represents a group represented by any one of Formula (2-10), Formula (2-11), Formula (2-12), Formula (2-13), Formula (3-10), Formula (3-11), Formula (3-12), Formula (3-13), Formula (4-10), Formula (4-11), Formula (5-10), and Formula (5-11), at least one of the response speed, the dependence of the response speed on the electric field strength, and the manufacturing applicability is more excellent. Further, from the comparison between Examples 1-1 to 1-10 and the comparison between Examples 1-25 to 1-28 and Examples 1-32 to 1-35 etc., it was confirmed that when D represents a group represented by Formula (2-11) or Formula (3-11), the dependence of the response speed on the electric field strength is further excellent.

[0621] From the results of Examples 1-12 to 1-13, Examples 1-30 to 1-31, Examples 1-43 to 1-44, Examples 1-56 to 1-57, and Example 1-63, it was confirmed that in a specific compound, when the group represented by Formula (A-1) is the group represented by Formula (C-1) or the group represented by Formula (C-2), the dependence of the response speed on the electric field strength is more excellent.

[0622] From the comparison between Examples 1-1 to 1-12 and Example 1-13 and the comparison between Examples 1-50 to 1-56 and Example 1-57 etc., it was confirmed that in a specific compound, when the group represented by Formula (A-1) is the group represented by Formula (A-2), the manufacturing applicability is more excellent.

[0623] From the comparison of Examples 1-1 to 1-11 and the comparison of Examples 1-50 to 1-55, etc., it was confirmed that in a specific compound, when Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 14 carbon atoms which may have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, or a halogen atom, the manufacturing applicability is further excellent.

[0624] Moreover, from the comparison of Examples 1-37 to 1-64, etc., it was confirmed that in a specific compound, when D represents a group represented by any one of Formula (4-10) and Formula (4-11), the dependence of the quantum efficiency on the electric field strength is more excellent. And from the comparison of Examples 1-37 to 1-49 and the comparison of Examples 1-65 to 1-74, etc., it was confirmed that in a specific compound, when D represents a group represented by any one of Formula (4-10) and Formula (4-11) and Rs represents a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may have a substituent, or a group represented by Formula (S1), the dependence of the quantum efficiency on the electric field strength is further excellent.

[0625] Symbol Explanation

[0626] 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, in this order, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein the photoelectric conversion film contains a compound represented by formula (1), In formula (1), D represents a group represented by any one of formulas (2) to (5). In formulas (2) to (5), * represents the bonding position, 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), in formula (A-1), * represents a bonding position In formulas (2) to (5), X 21 , X 31 , X 41 , X 42 , X 51 and X 52 Each independently represents a sulfur atom, an oxygen atom, NR X1 or CR X2 R X3 , R X1 ~R X3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group optionally having a substituent, or an aromatic ring group optionally having a substituent R X2 and R X3 optionally linked via a single bond or a divalent linking group, Y 21 、Y 22 、Y 23 、Y 24 、Y 31 、Y 32 、Y 33 、Y 34 、Y 41 、Y 42 、Y 51 and Y 52 each independently represents -CR Y1 = or a nitrogen atom, R Y1 represents a hydrogen atom or a substituent, Among them, In formula (2), Y 21 ~Y 24 at least one of which represents -CRs=; in formula (3), Y 31 ~Y 34 at least one of which represents -CRs=; in formula (4), Y 41 and Y 42 at least one of which represents -CRs=; and in formula (5), Y 51 and Y 52 at least one of which represents -CRs= Rs represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, an optionally substituted silyl group, a cyano group, or a halogen atom, In formula (A-1), C 1 represents a ring having 2 or more carbon atoms and optionally having substituents W 1 represents a sulfur atom, an oxygen atom, =NR W2 or =CR W3 R W4 , R W2 represents a hydrogen atom or a substituent, R W3 and R W4 each independently represents cyano, -SO2R W5 , -COOR W6 or -COR W7 , R W5 ~R W7 each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group or an optionally substituted aliphatic heterocyclic group.

2. The photoelectric conversion element according to claim 1, wherein, R Y1 represents a hydrogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, an aryl group optionally having a substituent, a heteroaryl group optionally having a substituent, an alkoxy group optionally having a substituent, an aryloxy group optionally having a substituent, an amino group optionally having a substituent, a silyl group optionally having a substituent, a cyano group or a halogen atom.

3. The photoelectric conversion element according to claim 1, wherein, D represents a group represented by any one of formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (4-10), (4-11), (5-10), and (5-11). In formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (4-10), (4-11), (5-10), and (5-11), * represents the bonding position, and Rs represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, an optionally substituted silyl group, a cyano group, or a halogen atom. X 21 , X 31 , X 41 , X 42 , X 51 and X 52 Each independently represents a sulfur atom, an oxygen atom, NR X1 or CR X2 R X3 , R X1 ~R X3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group optionally having a substituent, or an aromatic ring group optionally having a substituent Y 21 、Y 22 、Y 23 、Y 24 、Y 31 、Y 32 、Y 33 、Y 34 、Y 42 and Y 52 each independently represents -CR Y1 = or a nitrogen atom, and R Y1 represents a hydrogen atom or a substituent, 4. The photoelectric conversion element according to claim 3, wherein, Rs represents an optionally substituted linear alkyl group having 1 to 5 carbon atoms, an optionally substituted branched alkyl group having 3 to 7 carbon atoms, an optionally substituted cyclic alkyl group having 3 to 6 carbon atoms, an optionally substituted alkenyl group having 2 to 5 carbon atoms, an optionally substituted alkynyl group having 2 to 5 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, an optionally substituted heteroaryl group having 2 to 14 carbon atoms, an optionally substituted alkoxy group having 1 to 5 carbon atoms, an optionally substituted aryloxy group having 6 to 14 carbon atoms, an optionally substituted amino group, an optionally substituted silyl group, a cyano group, or a halogen atom.

5. The photoelectric conversion element according to claim 4, wherein, ​ D represents a group represented by any one of the following formulas: formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (3-10), formula (3-11), formula (3-12), formula (3-13), formula (5-10), and formula (5-11).

6. The photoelectric conversion element according to claim 1, wherein W 1 is an oxygen atom or a sulfur atom.

7. The photoelectric conversion element according to claim 6, wherein The group represented by formula (A-1) is the group represented by formula (A-2), In formula (A-2), * represents the bonding position, C 2 represents a ring having 3 or more carbon atoms and optionally having substituents W 2 and W 3 each independently represents an oxygen atom or a sulfur atom.

8. The photoelectric conversion element according to claim 7, wherein The group represented by formula (A-2) is the group represented by formula (C-1) or the group represented by formula (C-2), In formula (C-1) and formula (C-2), * represents the bonding position, In formula (C-1), C 3 represents an optionally substituted aromatic ring X c1 and X c2 each independently represents a sulfur atom or an oxygen atom, In formula (C-2), X c3 ~X c5 each independently represents a sulfur atom or an oxygen atom, R c1 and R c2 each independently represents a hydrogen atom or a substituent.

9. The photoelectric conversion element according to claim 8, wherein X c1 and X c2 are both oxygen atoms, X c3 and X c4 are both oxygen atoms.

10. The photoelectric conversion element according to any one of claims 1 to 9, wherein Rs represents a linear alkyl group having 1 to 5 carbon atoms which may optionally have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may optionally have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may optionally have a substituent, an aryl group having 6 to 14 carbon atoms which may optionally have a substituent, a heteroaryl group having 2 to 14 carbon atoms which may optionally have a substituent, an alkoxy group having 1 to 5 carbon atoms which may optionally have a substituent, an aryloxy group having 6 to 14 carbon atoms which may optionally have a substituent, a silyl group which may optionally have a substituent, or a halogen atom.

11. The photoelectric conversion element according to claim 4, wherein D represents the group represented by formula (4-10) or the group represented by formula (4-11).

12. The photoelectric conversion element according to claim 11, wherein Rs represents a linear alkyl group having 1 to 5 carbon atoms which may optionally have a substituent, a branched alkyl group having 3 to 7 carbon atoms which may optionally have a substituent, a cyclic alkyl group having 3 to 6 carbon atoms which may optionally have a substituent, or the group represented by formula (S1), In formula (S1), C m represents an aromatic hydrocarbon having 6 to 14 carbon atoms which may optionally have substituents R m represents a substituent * represents the bonding position.

13. The photoelectric conversion element according to any one of claims 1 to 9, 11, and 12, wherein The photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion film has a bulk heterojunction structure formed in a state where the compound represented by formula (1) and the n-type organic semiconductor are mixed.

14. The photoelectric conversion element according to claim 13, wherein The n-type organic semiconductor contains fullerenes selected from the group consisting of fullerene and its derivatives.

15. The photoelectric conversion element according to any one of claims 1 to 9, 11, and 12, wherein The photoelectric conversion film further contains a p-type organic semiconductor.

16. The photoelectric conversion element according to any one of claims 1 to 9, 11, and 12, wherein The photoelectric conversion film further contains a pigment.

17. The photoelectric conversion element according to any one of claims 1 to 9, 11, and 12, wherein, between the conductive film and the transparent conductive film, there is one or more intermediate layers in addition to the photoelectric conversion film.

18. An imaging element having the photoelectric conversion element according to any one of claims 1 to 9, 11, and 12.

19. An optical sensor having the photoelectric conversion element according to any one of claims 1 to 9, 11, and 12.

20. A method for manufacturing an imaging element, which includes a step of manufacturing the photoelectric conversion element according to any one of claims 1 to 9, 11, and 12.

21. A compound represented by formula (1), in formula (1), D represents a group represented by any one of formulas (2) to (5), and in formulas (2) to (5), * represents the bonding position, 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), in formula (A-1), * represents the bonding position in formulas (2) to (5), X 21 , X 31 , X 41 , X 42 , X 51 and X 52 Each independently represents a sulfur atom, an oxygen atom, NR X1 or CR X2 R X3 , R X1 ~R X3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group optionally having a substituent, or an aromatic ring group optionally having a substituent R X2 and R X3 optionally connected via a single bond or a divalent linking group, Y 21 、Y 22 、Y 23 、Y 24 、Y 31 、Y 32 、Y 33 、Y 34 、Y 41 、Y 42 、Y 51 and Y 52 each independently represents -CR Y1 = or a nitrogen atom, and R Y1 represents a hydrogen atom or a substituent, Among them, In formula (2), Y 21 ~Y 24 at least one of them represents -CRs=, in formula (3), Y 31 ~Y 34 at least one of them represents -CRs=, in formula (4), Y 41 and Y 42 at least one of them represents -CRs=, and in formula (5), Y 51 and Y 52 at least one of them represents -CRs=, Rs represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, an optionally substituted silyl group, a cyano group, or a halogen atom, in formula (A-1), C 1 represents a ring having 2 or more carbon atoms and optionally having substituents W 1 represents a sulfur atom, an oxygen atom, =NR W2 or =CR W3 R W4 , R W2 represents a hydrogen atom or a substituent, R W3 and R W4 each independently represents cyano, -SO2R W5 , -COOR W6 or -COR W7 , R W5 ~R W7 Each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group.

22. The compound according to claim 21, wherein, R Y1 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, an optionally substituted silyl group, a cyano group or a halogen atom.

23. The compound according to claim 21, wherein, D represents a group represented by any one of formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (4-10), (4-11), (5-10), and (5-11), in formulas (2-10), (2-11), (2-12), (2-13), (3-10), (3-11), (3-12), (3-13), (4-10), (4-11), (5-10), and (5-11), * represents the bonding position, X 21 , X 31 , X 21 , X 42 , X 51 and X 52 Each independently represents a sulfur atom, an oxygen atom, NR X1 or CR X2 R X3 , R X1 ~R X3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group optionally having a substituent, or an aromatic ring group optionally having a substituent Y 21 、Y 22 、Y 23 、Y 24 、Y 31 、Y 32 、Y 33 、Y 34 、Y 42 and Y 52 each independently represents -CR Y1 = or a nitrogen atom, and R Y1 represents a hydrogen atom or a substituent, Rs represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, an optionally substituted silyl group, a cyano group, or a halogen atom.

24. The compound according to claim 23, wherein, Rs represents a linear alkyl group having 1 to 5 carbon atoms which may optionally have substituents, a branched alkyl group having 3 to 7 carbon atoms which may optionally have substituents, a cyclic alkyl group having 3 to 6 carbon atoms which may optionally have substituents, an alkenyl group having 2 to 5 carbon atoms which may optionally have substituents, an alkynyl group having 2 to 5 carbon atoms which may optionally have substituents, an aryl group having 6 to 14 carbon atoms which may optionally have substituents, a heteroaryl group having 2 to 14 carbon atoms which may optionally have substituents, an alkoxy group having 1 to 5 carbon atoms which may optionally have substituents, an aryloxy group having 6 to 14 carbon atoms which may optionally have substituents, an amino group which may optionally have substituents, a silyl group which may optionally have substituents, a cyano group or a halogen atom.

25. The compound according to claim 24, wherein, D represents a group represented by any one of the formula (2-10), the formula (2-11), the formula (2-12), the formula (2-13), the formula (3-10), the formula (3-11), the formula (3-12), the formula (3-13), the formula (5-10) and the formula (5-11).

26. The compound according to claim 21, wherein, W 1 is an oxygen atom or a sulfur atom.

27. The compound according to claim 26, wherein, The group represented by the formula (A-1) is the group represented by the formula (A-2), In the formula (A-2), * represents the bonding position, C 2 represents a ring having 3 or more carbon atoms and optionally having substituents W 2 and W 3 each independently represents an oxygen atom or a sulfur atom.

28. The compound according to claim 27, wherein, The group represented by the formula (A-2) is the group represented by the formula (C-1) or the group represented by the formula (C-2), In the formula (C-1) and the formula (C-2), * represents the bonding position, In the formula (C-1), C 3 represents an optionally substituted aromatic ring X c1 and X c2 each independently represents a sulfur atom or an oxygen atom, In the formula (C-2), X c3 ~X c5 each independently represents a sulfur atom or an oxygen atom, R c1 and R c2 each independently represents a hydrogen atom or a substituent.

29. The compound according to claim 28, wherein, X c1 and X c2 are both oxygen atoms, X c3 and X c4 are both oxygen atoms.

30. The compound according to any one of claims 21 to 29, wherein, Rs represents a linear alkyl group having 1 to 5 carbon atoms which may optionally have substituents, a branched alkyl group having 3 to 7 carbon atoms which may optionally have substituents, a cyclic alkyl group having 3 to 6 carbon atoms which may optionally have substituents, an aryl group having 6 to 14 carbon atoms which may optionally have substituents, a heteroaryl group having 2 to 14 carbon atoms which may optionally have substituents, an alkoxy group having 1 to 5 carbon atoms which may optionally have substituents, an aryloxy group having 6 to 14 carbon atoms which may optionally have substituents, a silyl group which may optionally have substituents or a halogen atom.

31. The compound according to claim 24, wherein, D represents a group represented by the formula (4-10) or a group represented by the formula (4-11).

32. The compound according to claim 31, wherein, Rs represents a linear alkyl group having 1 to 5 carbon atoms which may optionally have substituents, a branched alkyl group having 3 to 7 carbon atoms which may optionally have substituents, a cyclic alkyl group having 3 to 6 carbon atoms which may optionally have substituents or a group represented by the formula (S1), In the formula (S1), C m represents an aromatic hydrocarbon having 6 to 14 carbon atoms which may optionally have substituents R m represents a substituent * represents the bonding position.

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