Compound, composition, ink, photoelectric conversion element, and optical sensor

Abstract

To provide a compound, a composition, an ink, a photoelectric conversion element, and an optical sensor in which a dark current in the photoelectric conversion element is suppressed.SOLUTION: A compound represented by the following formula (1): In formula (1), D1, D2, L1, L2, m, n, A1, and A2 are as defined in the description.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Photoelectric conversion elements are attracting attention as extremely useful devices from the viewpoints of, for example, energy conservation and reduction of carbon dioxide emissions.

[0003] A photoelectric conversion element is an element that includes at least a pair of electrodes consisting of an anode and a cathode, and an active layer disposed between the pair of electrodes. In a photoelectric conversion element, at least one of the pair of electrodes is made of a transparent or semitransparent material, and light is incident on the active layer from the transparent or semitransparent electrode side. The energy (hν) of light incident on the active layer generates charges (holes and electrons) in the active layer, and the generated holes move toward the anode and the electrons move toward the cathode. The charges that reach the anode and cathode are then extracted to the outside of the element.

[0004] In recent years, there has been a demand for further improvements in the properties of photoelectric conversion elements, and various semiconductor materials have been developed and reported to meet this demand.

[0005] Patent Document 1 discloses a compound having a specific chemical structure that can suppress a decrease in the external quantum efficiency of a photoelectric conversion element due to heat treatment and improve the heat resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-22138 Summary of the Invention [Problem to be solved by the invention]

[0007] However, there is a demand for further semiconductor materials that can satisfy the properties required for photoelectric conversion elements. The present disclosure has been made in view of the above, and relates to providing a compound, a composition, an ink, a photoelectric conversion element, and an optical sensor that suppress dark current in a photoelectric conversion element. [Means for solving the problem]

[0008] The present disclosure includes the following aspects. <1> A compound represented by the following formula (1):

[0009] [ka]

[0010] (In formula (1), D1 and D2 are each independently a polycyclic aromatic group having two bonds formed by condensing three or more monocyclic rings, wherein the conjugated structure connecting the two bonds in D1 and D2 at the shortest distance each contains four or more double bonds, and the number of single bonds in each monocyclic ring constituting the polycyclic aromatic group each independently is three or less; L1 and L2 each independently represent an aromatic group having two bonds, and each independently represent three or less double bonds contained in a conjugated structure connecting the two bonds in L1 and L2 by the shortest distance, and L1 and L2 may be the same or different, and are different from D1 and D2, m and n each independently represent an integer of 1 to 3; A1 and A2 each independently represent an electron-withdrawing monovalent group having at least one aromatic ring. <2> D1 and D2 have the same main skeleton; <1> The compound described in <3> D1 and D2 are donor groups; <1> or <2> The compound described in <4> D1, D2, L1, and L2 each have a thiophene structure; <1> ~ <3> 1. The compound according to any one of claims 1 to 9. <5> D1 and D2 are polycyclic aromatic groups having fused 5-membered rings. <1> ~ <4> 1. The compound according to any one of claims 1 to 9. <6> D1 and D2 do not contain an oxygen atom in the main skeleton. <1> ~ <5> 1. The compound according to any one of claims 1 to 9. <7> The polycyclic aromatic groups in D1 and D2 each independently have at least one of an sp3 carbon and an sp3 silicon, and a side chain is bonded to the sp3 carbon or sp3 silicon. <1> ~ <6> 1. The compound according to any one of claims 1 to 9. <8> D1 and D2 each independently represent any one of groups represented by the following formulae (D-1) to (D-7): <1> ~ <7> 1. The compound according to any one of claims 1 to 9.

[0011] [ka]

[0012] (In formula (D-1), formula (D-2), formula (D-6) and formula (D-7), X is a group represented by the following formula (X-1) or formula (X-2).

[0013] [ka]

[0014] In formulas (D-3) to (D-7), (X-1) and (X-2), R d are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In formula (D-2), formula (D-5), and formula (D-7), Ar 1 and Ar 2 are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. 1 and Ar 2 Either one of them may not be present.) <9> m and n are 1; <1> ~ <8> 1. The compound according to any one of claims 1 to 9. <10> the conjugated structure connecting the two bonds in L1 and L2 by the shortest distance each independently contains two or less double bonds; <1> ~ <9> 1. The compound according to any one of claims 1 to 9. <11> A1 and A2 each independently represent any one of groups represented by the following formulae (a-1) to (a-8): <1> ~ <10> 1. The compound according to any one of claims 1 to 9.

[0015] [ka]

[0016] (In formulas (a-1) to (a-8), R a1 ~R a6 are each independently a hydrogen atom, a halogen atom, or a cyano group. <12> The semiconductor material includes a p-type semiconductor material and an n-type semiconductor material, <1> ~ <11> A composition comprising a compound according to any one of claims 1 to 4. <13> The p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): <12> The composition described in

[0017] [ka]

[0018] (In formula (3), Ar 3 and Ar 4 each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7).

[0019] [ka]

[0020] In formulas (Z-1) to (Z-7), R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different, In formula (4), Ar 5 represents a divalent aromatic heterocyclic group. <14> <1> ~ <13> 10. An ink comprising the compound according to any one of the above items and a solvent. <15> an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material; The n-type semiconductor material is <1> ~ <14> A photoelectric conversion element comprising the compound according to any one of the above items. <16> A photodetector element, <15> The photoelectric conversion element according to claim 1. <17> <15> or <16> An optical sensor comprising the photoelectric conversion element according to claim 1. [Effects of the Invention]

[0021] According to the present disclosure, there are provided a compound, composition, ink, photoelectric conversion element, and optical sensor that suppress dark current in a photoelectric conversion element. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element. DETAILED DESCRIPTION OF THE INVENTION

[0023] An embodiment of the present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiment. In the following disclosure, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0024] The compounds of the present disclosure will be described below, and further, a photoelectric conversion element using the compounds of the present disclosure will be described with reference to the drawings. Note that the drawings merely show the shapes, sizes, and arrangements of the components to the extent that the invention can be understood. The present disclosure is not limited by the following description, and each component can be appropriately modified within the scope of the present disclosure. Furthermore, the configuration of the present disclosure is not necessarily manufactured or used in the arrangement shown in the drawings.

[0025] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the lower and upper limits, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, when a composition contains multiple substances corresponding to each component, the content of each component in the composition means the total content of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, when multiple elements are listed using "or" or "or," unless otherwise expressly stated, it does not exclude the selection of a combination of the multiple elements unless a technical contradiction arises. In the present disclosure, even if an element is referred to in the singular, unless expressly stated otherwise, it does not exclude the presence of a plurality insofar as it does not create a technical contradiction. In the present disclosure, multiple exemplary aspects described separately may be combined with each other to form a new aspect, unless they contradict each other.

[0026] The following describes commonly used terms in this disclosure. In the description of this disclosure, the following descriptions apply unless otherwise specified.

[0027] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0028] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0029] "Polymer compounds" are compounds that have a molecular weight distribution and have a number average molecular weight equivalent to polystyrene of 1 x 10 3 More than 1×10 8 The term "polymer" refers to a polymer having the following structure: The total amount of structural units contained in the polymer compound is 100 mol %.

[0030] The term "structural unit" refers to a residue derived from a raw material compound (monomer), of which one or more are present in a compound or polymer compound.

[0031] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0032] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0033] In the present disclosure, "side chain A" refers to hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or nitro group, This means that

[0034] In the present disclosure, "side chain B" refers to the group options in the above "side chain A" excluding hydrogen atoms.

[0035] The embodiment in which "may have a substituent" includes both a case in which all hydrogen atoms constituting the compound or group are unsubstituted, and a case in which one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0036] Examples of the "substituent" include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an alkyloxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. In this specification, the number of carbon atoms generally does not include the number of carbon atoms of substituents.

[0037] In this specification, unless otherwise specified, the "alkyl group" may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkyl group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. The number of carbon atoms in a branched or cyclic alkyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 50, more preferably 3 to 30, and even more preferably 4 to 20.

[0038] Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, a 2-ethylbutyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a cyclohexylmethyl group, a cyclohexylethyl group, an n-octyl group, a 2-ethylhexyl group, a 3-n-propylheptyl group, an adamantyl group, an n-decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-n-hexyl-decyl group, an n-dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group.

[0039] The alkyl group may have a substituent. The substituted alkyl group is, for example, a group in which a hydrogen atom in the above-exemplified alkyl group is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

[0040] Specific examples of the alkyl having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3-(4-methylphenyl)propyl group, a 3-(3,5-dihexylphenyl)propyl group, and a 6-ethyloxyhexyl group.

[0041] The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0042] Examples of cycloalkyl groups include unsubstituted alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group, as well as groups in which the hydrogen atoms in these groups are substituted with substituents such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0043] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0044] The term "aromatic carbocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon that may have a substituent. The aromatic carbocyclic group may further have a substituent. The term "aromatic carbocyclic ring" also includes a structure in which two or more carbocyclic rings (aromatic rings) are connected together via, for example, a group (substituent) containing a heteroatom.

[0045] Specific examples of the aromatic carbocyclic ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring.

[0046] The term "aryl group" refers to a monovalent aromatic carbocyclic group, which is the atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring from an aromatic hydrocarbon which may have a substituent.

[0047] The aryl group may have a substituent. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0048] The term "arylene group" refers to a divalent aromatic carbocyclic group, which is an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent.

[0049] The "alkyloxy group" (alkoxy group) may be linear, branched, or cyclic. The number of carbon atoms in a linear alkyloxy group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkyloxy group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0050] The alkyloxy group may have a substituent. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group, an n-decyloxy group, a 3,7-dimethyloctyloxy group, a 3-heptyldodecyloxy group, a lauryloxy group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0051] The cycloalkyl group in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group, not including the number of carbon atoms of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0052] Examples of the cycloalkyloxy group include unsubstituted cycloalkyloxy groups such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group, as well as groups in which a hydrogen atom in these groups has been substituted with a fluorine atom or an alkyl group.

[0053] The number of carbon atoms in the "aryloxy group" is usually preferably 6 to 60, and more preferably 6 to 48, not including the number of carbon atoms of the substituent.

[0054] The aryloxy group may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0055] The "alkylthio group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkylthio group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkylthio group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0056] The alkylthio group may have a substituent. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

[0057] The cycloalkyl group in the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms in the cycloalkylthio group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0058] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0059] The number of carbon atoms in the "arylthio group" is usually preferably 6 to 60, and more preferably 6 to 48, not including the number of carbon atoms in the substituent.

[0060] The arylthio group may have a substituent. Examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group (C1-C12 indicates that the group immediately following it has 1 to 12 carbon atoms, and the same applies below), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

[0061] The term "heterocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an optionally substituted heterocyclic compound.

[0062] The heterocyclic group may further have a substituent. The number of carbon atoms in the heterocyclic group is usually preferably 2 to 30, more preferably 2 to 6, not including the number of carbon atoms in the substituent.

[0063] Examples of substituents that the heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group. The heterocyclic group includes an "aromatic heterocyclic group."

[0064] The term "aromatic heterocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an aromatic heterocyclic compound which may have a substituent. The aromatic heterocyclic group may further have a substituent.

[0065] Specific examples of the aromatic heterocycle include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring.

[0066] Aromatic heterocyclic compounds include compounds in which the heterocycle itself exhibits aromaticity, as well as compounds in which an aromatic ring is condensed with a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0067] Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

[0068] Among aromatic heterocyclic compounds, specific examples of compounds in which the aromatic heterocycle itself does not exhibit aromaticity and an aromatic ring is condensed with the heterocycle include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0069] The number of carbon atoms in the monovalent heterocyclic group is usually preferably 2 to 60, and more preferably 4 to 20, not including the number of carbon atoms in the substituent.

[0070] The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group, a triazinyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, or the like.

[0071] The term "substituted amino group" refers to an amino group having a substituent. Examples of the substituent on the amino group include an alkyl group, an aryl group, and a monovalent heterocyclic group, and an alkyl group, an aryl group, or a monovalent heterocyclic group is preferred. The number of carbon atoms in the substituted amino group is usually preferably 2 to 30.

[0072] Examples of the substituted amino group include dialkylamino groups such as a dimethylamino group and a diethylamino group; and diarylamino groups such as a diphenylamino group, a bis(4-methylphenyl)amino group, a bis(4-tert-butylphenyl)amino group, and a bis(3,5-di-tert-butylphenyl)amino group.

[0073] The "acyl group" may have a substituent. The number of carbon atoms in the acyl group, not including the number of carbon atoms in the substituent, is usually preferably 2 to 20, and more preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

[0074] The term "imine residue" refers to the atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon-nitrogen double bond from an imine compound. The term "imine compound" refers to an organic compound having a carbon-nitrogen double bond within the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atom bonded to the nitrogen atom constituting the carbon-nitrogen double bond in an aldimine is substituted with an alkyl group or the like.

[0075] The imine residue usually preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the structural formula described in paragraph

[0058] of WO 2023 / 100844. In the structural formula, Me represents a methyl group.

[0076] The term "amide group" refers to the atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an amide. The number of carbon atoms in the amide group is usually preferably 1 to 20, and more preferably 1 to 18. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyromido group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyromido group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

[0077] The term "acid imide group" refers to the atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is usually preferably 4 to 20. Specific examples of the acid imide group include groups represented by the structural formula described in paragraph

[0061] of WO 2023 / 100844. In the structural formula, Me represents a methyl group.

[0078] A "substituted carbonyl group" is a -(C=O)-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0079] "Substituted oxycarbonyl group" means -(C=O)-OR X or -O-(C=O)-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0080] "Substituted sulfonyl group" means -SO2-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0081] "Substituted oxysulfonyl group" means -(SO2)-OR X or -O-(SO2)-R Xwhere R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0082] The number of carbon atoms in the substituted oxycarbonyl group is usually preferably 2 to 60, more preferably 2 to 48, not including the number of carbon atoms in the substituent.

[0083] Specific examples of the substituted oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl group, a dodecyloxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.

[0084] The "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkenyl group, not including the number of carbon atoms in the substituent, is usually preferably 2 to 30, more preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkenyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 4 to 20.

[0085] The alkenyl group may have a substituent. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0086] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group, not including the number of carbon atoms in the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0087] Examples of the cycloalkenyl group include unsubstituted cycloalkenyl groups such as a cyclohexenyl group, and groups in which a hydrogen atom in these groups has been substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0088] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0089] The "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkynyl group, not including the number of carbon atoms in the substituent, is usually preferably 2 to 20, more preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkynyl group, not including the number of carbon atoms in the substituent, is usually preferably 4 to 30, more preferably 4 to 20.

[0090] The alkynyl group may have a substituent. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0091] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group, not including the number of carbon atoms of the substituent, is usually preferably 4 to 30, and more preferably 12 to 19.

[0092] Examples of the cycloalkynyl group include unsubstituted cycloalkynyl groups such as a cyclohexynyl group, and groups in which the hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, or fluorine atoms.

[0093] Examples of the substituted cycloalkynyl group include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0094] The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0095] The symbol "*" in a chemical formula represents a bond. A dotted line in a chemical formula also represents a bond. When a chemical formula contains two symbols "*" or two dotted lines, there is no particular limitation as to which of the two bonds the "*" and dotted line represent.

[0096] "Ink" refers to a liquid used in a coating method, and is not limited to a colored liquid. Furthermore, "coating method" encompasses methods for forming a film (layer) using a liquid substance, such as slot die coating, slit coating, knife coating, spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, and capillary coating.

[0097] The ink may be a solution or a dispersion such as an emulsion or suspension.

[0098] The "peak absorption wavelength" is a parameter determined based on the absorption peak of an absorption spectrum measured in a predetermined wavelength range, and refers to the wavelength of the absorption peak with the greatest absorbance among the absorption peaks of the absorption spectrum.

[0099] "External quantum efficiency" is also called EQE (External Quantum Efficiency), and refers to the ratio (%) of the number of electrons that can be extracted outside the photoelectric conversion element out of the number of electrons generated relative to the number of photons irradiated onto the photoelectric conversion element.

[0100] ≪Compound≫ The compound of the present disclosure is represented by the following formula (1):

[0101] [ka]

[0102] (In formula (1), D1 and D2 are each independently a polycyclic aromatic group having two bonds formed by condensing three or more monocyclic rings, wherein the conjugated structure connecting the two bonds in D1 and D2 at the shortest distance each contains four or more double bonds, and the number of single bonds in each monocyclic ring constituting the polycyclic aromatic group each independently is three or less; L1 and L2 each independently represent an aromatic group having two bonds, and each independently represent three or less double bonds contained in a conjugated structure connecting the two bonds in L1 and L2 by the shortest distance, and L1 and L2 may be the same or different, and are different from D1 and D2, m and n each independently represent an integer of 1 to 3; A1 and A2 each independently represent an electron-withdrawing monovalent group having at least one aromatic ring.

[0103] The compound of the present disclosure suppresses dark current in a photoelectric conversion element. The action of the compounds of the present disclosure is presumed to be as follows.

[0104] In the compound of the present disclosure, represented by formula (1), the groups represented by D1 and D2 are each a core, the groups represented by L1 and L2 are each a linker, and the groups represented by A1 and A2 are each an acceptor. In the compounds of the present disclosure, each of the ring structures (which may be either a monocyclic structure or a fused ring structure) having two bonds and included in the main skeleton chemical structure connecting A1 and A2 by the shortest distance is considered to be one unit. That is, A1, L1, D1, D2, L2, and A2 are each considered to be one structural unit, and the structural unit is referred to as a unit.

[0105] The dark current in a photoelectric conversion element is caused by the current due to the impurity potential in the injection current or the current due to the band-to-band transition, and by the current due to the broadening of the density of states (DOS). In particular, when the DOS broadens, electrons flow more easily, increasing the dark current value. Therefore, in order to reduce the dark current, it is necessary to narrow the broadening of the DOS.

[0106] Since the compound of the present disclosure consists of two units D1 and D2 as the core, and the chemical structures of the main skeletons of D1 and D2 are kept planar, the aggregation state of the compounds is appropriately controlled, and the broadening of DOS becomes narrow, so that the dark current in the photoelectric conversion device can be reduced. Note that the present disclosure is not limited to the above estimation mechanism at all.

[0107] <D1 and D2; core> [Polycyclic aromatic group] In formula (1), D1 and D2 are each independently a polycyclic aromatic group having two bonds with three or more monocycles fused (that is, a divalent polycyclic aromatic group having three or more rings).

[0108] The polycyclic aromatic groups in D1 and D2 may each independently be either a polycyclic aromatic heterocyclic group or a polycyclic aromatic carbocyclic group. From the viewpoint of being likely to absorb light with a long wavelength, a polycyclic aromatic heterocyclic group is preferred. The heteroatom in the polycyclic aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, more preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a nitrogen atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the polycyclic aromatic groups in D1 and D2 preferably have a sulfur-containing heterocycle, and more preferably are sulfur-containing heterocyclic groups.

[0109] The polycyclic aromatic groups in D1 and D2 are each independently a polycyclic aromatic group with three or more monocycles fused. From the viewpoint of ease of synthesis, it is preferably a polycyclic aromatic group with 3 to 8 monocycles fused, more preferably a polycyclic aromatic group with 3 to 6 monocycles fused, even more preferably a polycyclic aromatic group with 3 to 4 monocycles fused, and most preferably a polycyclic aromatic group with 3 monocycles fused.

[0110] From the viewpoint of ease of synthesis, D1 and D2 are preferably polycyclic aromatic groups having fused 5- or 6-membered rings, may be polycyclic aromatic groups having fused 5- and 6-membered rings, and are more preferably polycyclic aromatic groups having fused 5-membered rings.

[0111] From the viewpoint of absorbing longer wavelengths, D1 and D2 preferably have a thiophene structure, more preferably have a thiophene structure in the main skeleton, that is, D1 and D2 are preferably each independently a polycyclic aromatic group in which a ring containing a thiophene ring is condensed.

[0112] From the viewpoint of reducing dark current, it is preferable that D1 and D2 do not contain oxygen atoms in the main skeleton. That is, the main skeleton of D1 and D2 preferably consists of hydrogen atoms, carbon atoms, and sulfur atoms, or preferably consists of hydrogen atoms, carbon atoms, and nitrogen atoms, and more preferably consists of hydrogen atoms, carbon atoms, and sulfur atoms.

[0113] From the viewpoint of reducing dark current in a photoelectric conversion element, it is preferable that D1 and D2 have the same main skeleton, and it is more preferable that D1 and D2 have the same chemical structure. That is, D1 and D2 may have different side chains. In the present disclosure, the main skeleton (also referred to as the mother skeleton) refers to a chemical structure represented only by a ring structure (such as a single ring or a fused ring).

[0114] The number of double bonds contained in the conjugated structure connecting the two bonds in D1 and D2 by the shortest distance is each independently 4 or more. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of double bonds contained in the conjugated structure connecting the two bonds by the shortest distance is each independently preferably 4 to 10, more preferably 4 to 8, even more preferably 4 to 6, still more preferably 4 or 5, and even more preferably 4.

[0115] The number of single bonds in each single ring constituting the polycyclic aromatic group in D1 and D2 is independently 3 or less. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of single bonds in each single ring constituting the polycyclic aromatic group is preferably 2 or 3, and more preferably 3.

[0116] That is, it is preferable that D1 and D2 have, in the shortest conjugated structure connecting the two bonds between them and the two adjacent structural units, four or more double bonds contained in the conjugated structure connecting the two bonds at the shortest distance, and that the number of chains of single bonds not involved in the conjugation connecting, at the shortest distance, the sp2 carbons forming the consecutive double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is two or less.

[0117] From the viewpoint that the compound easily absorbs light of a long wavelength, D1 and D2 are preferably donor groups (also referred to as groups with donating properties).

[0118] [Side chain] In the formula (1), it is preferable that the polycyclic aromatic group in D1 and D2 has a side chain. In the present disclosure, the side chain refers to a group bonded to an atom constituting the main skeleton (such as a single ring or a fused ring). In D1 and D2, the side chain possessed by the polycyclic aromatic group is preferably the "side chain B" of the present disclosure.

[0119] In D1 and D2, the side chain preferably has an aromatic ring or a branched chain, and more preferably has a branched chain.

[0120] In D1 and D2, the polycyclic aromatic group may have a plurality of side chains, and when it has a plurality of side chains, the plurality of side chains may be the same or different from each other.

[0121] In D1 and D2, when a plurality of side chains are present, each side chain is preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group, which may have a substituent, more preferably an alkyl group or an aryl group, which may have a substituent, and even more preferably an alkyl group.

[0122] In D1 and D2, the side chain preferably has 2 or more carbon atoms, more preferably 2 to 30 carbon atoms, even more preferably 3 to 20 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0123] The polycyclic aromatic groups in D1 and D2 each independently preferably have at least one of sp3 carbon and sp3 silicon, more preferably sp3 carbon or sp3 silicon, and even more preferably sp3 carbon. The main skeletons of the polycyclic aromatic groups in D1 and D2 each independently preferably have at least one of sp3 carbon and sp3 silicon, more preferably sp3 carbon or sp3 silicon, and even more preferably sp3 carbon.

[0124] From the viewpoint of reducing dark current in a photoelectric conversion element, the side chains of the polycyclic aromatic groups in D1 and D2 are preferably bonded to sp3 carbon or sp3 silicon, more preferably sp3 carbon. When the side chains are bonded to sp3 atoms, the side chains protrude perpendicularly to the π-plane of the ring structure of the polycyclic aromatic group containing sp3 atoms in the main skeleton, which limits the pattern of association between molecules of the compound of the present disclosure and narrows the DOS.

[0125] [Chemical structures of D1 and D2] From the viewpoint that the compound easily absorbs light of a long wavelength, in the formula (1), D1 and D2 are each preferably independently any of the groups represented by the following formulas (D-1) to (D-7), and more preferably a group represented by the following formula (D-1) or (D-2). In the following formulas (D-1) to (D-7), the symbol "*" represents a bond to an adjacent unit, for example, when the following formula is D1, it represents a bond to L1 or D2, and when the following formula is D2, it represents a bond to D1 or L2. There are no particular restrictions on which bonds each of the two symbols "*" in a chemical formula represents.

[0126] [ka]

[0127] (X) In formula (D-1), formula (D-2), formula (D-6), and formula (D-7), X is a group represented by the following formula (X-1) or formula (X-2): From the viewpoint that the compound easily absorbs light of a long wavelength, X is more preferably a group represented by formula (X-1).

[0128] [ka]

[0129] (R d ) In formulas (D-3) to (D-7), (X-1) and (X-2), R d each independently represents the "side chain A" of the present disclosure. The polycyclic aromatic group in D1 and D2 preferably has a side chain, and in Formulas (D-3) to (D-7), Formula (X-1) and Formula (X-2), a plurality of R d At least one of these is preferably not a hydrogen atom.

[0130] In each of the formulas (D-3) to (D-7), (X-1) and (X-2), R d If there are two, then two R d may be the same or different from each other. In formulas (D-3) to (D-7), (X-1) and (X-2), R dare each independently preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group, which may have a substituent, more preferably an alkyl group or an aryl group, which may have a substituent, and even more preferably an alkyl group.

[0131] (Ar 1 and Ar 2 ) In formula (D-2), formula (D-5), and formula (D-7), Ar 1 and Ar 2 are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. 1 and Ar 2 Either one of them may not be present.

[0132] Ar 1 and Ar 2 The aromatic heterocycle that can constitute the above ring includes not only a single ring and a fused ring in which the heterocycle itself exhibits aromaticity, but also a ring in which an aromatic ring is fused to a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0133] Ar 1 and Ar 2 The aromatic heterocycles that can constitute the above may each be a single ring or a fused ring. When the aromatic heterocycle is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the rings may be fused rings having aromaticity. When these rings have multiple substituents, these substituents may be the same or different.

[0134] Ar 1 and Ar 2Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0135] Ar 1 and Ar 2 Specific examples of aromatic heterocycles that can constitute the above include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0136] (Examples of D1 and D2) Examples of formula (D-1) include groups represented by the following formulae (d-1-1) to (d-1-2). Examples of formula (D-2) include groups represented by the following formulae (d-2-1) to (d-2-10). Examples of formula (D-3) include groups represented by the following formulae (d-3-1) to (d-3-4). Examples of formula (D-4) include groups represented by the following formulae (d-4-1) to (d-4-2). Examples of formula (D-5) include groups represented by the following formulae (d-5-1) to (d-5-10). Examples of formula (D-6) include groups represented by the following formulae (d-6-1) to (d-6-2). Examples of formula (D-7) include groups represented by the following formulae (d-7-1) to (d-7-9).

[0137] In addition, in formulas (d-1-1) to (d-1-2), formulas (d-2-1) to (d-2-10), formulas (d-3-1) to (d-3-4), formulas (d-4-1) to (d-4-2), formulas (d-5-1) to (d-5-10), formulas (d-6-1) to (d-6-2), and formulas (d-7-1) to (d-7-9), R d1 The definition of R d is the same as the definition of In the following formulas (d-2-1) to (d-2-12), (d-5-1) to (d-5-10), and (d-7-1) to (d-7-9), U each independently represents CR d1 2, S, SiR d1 2, Se, NR d1 or O. U represents S or NR d1 It is preferable that: In the following formulas (d-1-1) to (d-1-2), (d-2-1) to (d-2-10), (d-3-1) to (d-3-4), (d-4-1) to (d-4-2), (d-5-1) to (d-5-10), (d-6-1) to (d-6-2), and (d-7-1) to (d-7-9), the symbol "*" represents a bond to an adjacent unit; for example, when the following formula is D1, it is a bond to L1 or D2, and when the following formula is D2, it is a bond to D1 or L2.

[0138] In view of the compound's tendency to absorb light of a long wavelength, D1 and D2 are each independently Preferably, it is a group represented by formula (d-1-1), formula (d-2-1) to formula (d-2-3), formula (d-3-1) to formula (d-3-4), formula (d-4-1) to formula (d-4-2), formula (d-5-1), formula (d-5-3), formula (d-6-1), formula (d-6-2), or formula (d-7-2) to formula (d-7-5), More preferably, it is a group represented by formula (d-1-1), formula (d-2-1) to formula (d-2-3), formula (d-3-4), formula (d-4-1) to formula (d-4-2), formula (d-6-1) or formula (d-6-2), More preferably, it is a group represented by formula (d-1-1), formula (d-2-3), formula (d-4-1) to formula (d-4-2), or formula (d-6-1).

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] (Specific examples of D1 and D2) Specific examples of D1 and D2 include groups represented by the following formulae. In each formula, the symbol "*" represents a bond to the adjacent unit; for example, when the formula below is D1, it represents a bond to L1 or D2, and when the formula below is D2, it represents a bond to D1 or L2. "**" represents a bond to the chemical structure shown on the left side of each formula. In the formula, R d1 When there are multiple R groups, they may be the same or different. d1 exists and R d1 When multiple examples of R are listed, any of the R in the chemical structure shown on the left side of each example may be used.d1 is R d1 There is no particular limitation on which of the examples of R it is, meaning that all combinations are included as preferred embodiments.

[0147] [Chemical formula]

[0148] [Chemical formula]

[0149] [Chemical formula]

[0150] [Chemical formula]

[0151] [Chemical formula]

[0152] [Combination of D1 and D2] The combination of D1 and D2 is not particularly limited. However, as described above, from the perspective of reducing the dark current in the photoelectric conversion element, it is preferable that D1 and D2 have the same main skeleton, and it is more preferable that D1 and D2 have the same chemical structure.

[0153] As the combination of D1 and D2, it is preferable that both are groups represented by formula (d-1-1), both are groups represented by formula (d-4-1), or both are groups represented by formula (d-2-1).

[0154] [L1 and L2; Linker] [Aromatic group] In formula (1), L1 and L2 are each independently an aromatic group having two bonds (i.e., a divalent aromatic group). Note that L1 and L2 do not have the same chemical structure as D1 and D2, but have different chemical structures.

[0155] The aromatic groups in L1 and L2 each preferably independently have a monocyclic or fused ring main skeleton. The aromatic groups in L1 and L2 may be either aromatic heterocyclic groups or aromatic carbocyclic groups, and aromatic heterocyclic groups are preferred from the viewpoint of absorbing long wavelength light. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of sulfur atom, silicon atom, selenium atom, nitrogen atom, and oxygen atom, more preferably at least one selected from the group consisting of sulfur atom, nitrogen atom, and oxygen atom, and even more preferably sulfur atom. That is, the aromatic groups in L1 and L2 preferably have a sulfur-containing heterocycle, more preferably a sulfur-containing heterocyclic group, and even more preferably a sulfur-containing heterocyclic group.

[0156] From the viewpoint of absorbing longer wavelengths, L1 and L2 preferably have a thiophene structure, and more preferably the main skeleton is made of a thiophene structure.

[0157] The number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance in the aromatic groups having two bonds in L1 and L2 is each independently 3 or less. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is preferably 1 to 3, more preferably 2 or less, even more preferably 1 or 2, and even more preferably 2.

[0158] L1 and L2 may have the same chemical structure or different chemical structures.

[0159] Specifically, L1 and L2 are atomic groups remaining after removing two hydrogen atoms from an aromatic compound which may have a substituent. Here, the aromatic compound also includes compounds having fused rings in which multiple ring structures are fused.

[0160] The number of carbon atoms in the main skeleton of the divalent aromatic carbocyclic group represented by L1 and L2 (i.e., the number of carbon atoms in the divalent aromatic carbocyclic group, not including the number of carbon atoms in the substituents) is usually preferably 6 to 60, more preferably 6 to 20, and even more preferably 6 to 10. The number of carbon atoms in the aromatic carbocyclic group, including the substituents, is usually preferably 6 to 100.

[0161] Examples of the divalent aromatic carbocyclic group represented by L1 and L2 include the divalent aromatic carbocyclic group represented by the following formula: The divalent aromatic carbocyclic group represented by the following formula may further have a substituent.

[0162] [ka]

[0163] The divalent aromatic heterocyclic group represented by L1 and L2 usually preferably has 2 to 60 carbon atoms, more preferably 4 to 60 carbon atoms, and even more preferably 4 to 20 carbon atoms.

[0164] Examples of the substituent that the divalent aromatic heterocyclic group represented by L1 and L2 may have include the "side chain B" of the present disclosure.

[0165] Specific examples of the divalent aromatic heterocyclic groups represented by L1 and L2 include divalent aromatic heterocyclic groups represented by the following formulas: These groups may further have a substituent.

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] The aromatic groups in L1 and L2 may have a side chain. In L1 and L2, the side chains are each independently preferably the "side chain B" of the present disclosure.

[0170] The aromatic groups in L1 and L2 may have multiple side chains, and when they have multiple side chains, the multiple side chains may be the same or different from each other.

[0171] When there are multiple side chains of the aromatic group in L1 and L2, each independently is preferably an alkyl group, cycloalkyl group, aryl group, alkyloxy group, cycloalkyloxy group, aryloxy group, amido group, substituted amino group, substituted oxycarbonyl group, alkylthio group, cycloalkylthio group, or arylthio group, which may have a substituent; more preferably an alkyl group, aryl group, alkyloxy group, substituted amino group, substituted oxycarbonyl group, or alkylthio group, even more preferably an alkyl group, alkyloxy group, substituted oxycarbonyl group, or alkylthio group, and still more preferably an alkyl group, alkyloxy group, substituted oxycarbonyl group, or alkylthio group.

[0172] [Chemical structures of L1 and L2] From the viewpoint of easily reducing the dark current of a photoelectric conversion element using a compound of the present disclosure, in the formula (1), L1 and L2 are each independently preferably any of the groups represented by the following formulae (L1-1) to (L1-9), more preferably any of the groups represented by the following formulae (L1-1) to (L1-7), and even more preferably any of the groups represented by the following formulae (L1-1) to (L1-4). In each formula, the dotted line represents a bond to an adjacent unit; for example, when the formula is L1, it represents a bond to A1, L1, or D1, and when the formula is L2, it represents a bond to D2, L2, or A2. That is, from the viewpoint of easily reducing the dark current of the photoelectric conversion element and easily absorbing light of a long wavelength, L1 and L2 each independently preferably have a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure, and more preferably have a thiophene structure, a thienothiophene structure, or a thiazole structure.

[0173] [ka]

[0174] In formulas (L1-1) to (L1-9), R L1 each independently represents a "side chain A" of the present disclosure. In formulas (L1-1) to (L1-9), R L1 are each independently preferably a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group, an amido group, a substituted amino group, a substituted oxycarbonyl group, an alkylthio group, a cycloalkylthio group, or an arylthio group, more preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group, an alkyloxy group, a substituted amino group, a substituted oxycarbonyl group, or an alkylthio group, even more preferably a hydrogen atom, an alkyl group, an alkyloxy group, a substituted oxycarbonyl group, or an alkylthio group, and still more preferably a hydrogen atom, an alkyl group, an alkyloxy group, a substituted oxycarbonyl group, or an alkylthio group.

[0175] The aromatic groups in L1 and L2 each preferably contain an element capable of non-covalent interaction with an element in an adjacent unit, which may be either one of the adjacent units or both adjacent units.

[0176] The non-covalent interaction is preferably an interaction between a sulfur atom and an oxygen atom, a sulfur atom and a fluorine atom, a sulfur atom and a chlorine atom, a sulfur atom and a nitrogen atom, a sulfur atom and a sulfur atom, a selenium atom and an oxygen atom, a selenium atom and a nitrogen atom, a selenium atom and a fluorine atom, a selenium atom and a sulfur atom, or a selenium atom and a chlorine atom.

[0177] The element that may be contained in the aromatic group in L1 and L2 and that can form a non-covalent interaction with an element in the adjacent unit is preferably at least one atom selected from the group consisting of a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, and a phosphorus atom, more preferably at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, and a nitrogen atom, even more preferably at least one of a sulfur atom and an oxygen atom, and particularly preferably an oxygen atom.

[0178] Similarly, the units adjacent to L1 and L2 preferably have at least one atom selected from the group consisting of halogen atoms, sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, and phosphorus atoms.

[0179] From the viewpoint of enabling non-covalent interactions, when the aromatic group in L1 or L2 has a sulfur atom, it is preferable that the unit adjacent to L1 or L2 has at least one atom selected from the group consisting of an oxygen atom, a halogen atom, a sulfur atom, and a nitrogen atom. When the aromatic group in L1 or L2 has an oxygen atom, the unit adjacent to L1 or L2 preferably has at least one atom selected from the group consisting of a sulfur atom, a selenium atom, and a phosphorus atom. When the aromatic group in L1 or L2 has a fluorine atom, the unit adjacent to L1 or L2 preferably has at least one atom selected from the group consisting of a sulfur atom, a selenium atom, and a phosphorus atom. When the aromatic group in L1 or L2 has a nitrogen atom, the unit adjacent to L1 or L2 preferably has at least one atom selected from the group consisting of a sulfur atom, a selenium atom, and a phosphorus atom. When the aromatic group in L1 or L2 has a selenium atom, the unit adjacent to L1 or L2 preferably has at least one of a sulfur atom, a selenium atom, an oxygen atom, and a nitrogen atom. When the aromatic group in L1 or L2 has a phosphorus atom, the unit adjacent to L1 or L2 preferably has an oxygen atom.

[0180] At least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a halogen atom, a nitrogen atom, a selenium atom, and a phosphorus atom may be contained in the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 or L2, or may be contained in a side chain bonded to the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 or L2, and L1 may be included in The non-covalent interaction may be formed between the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 or L2 and a side chain bonded to the main skeleton of the unit adjacent to L1 or L2, and R bonded to the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 or L2 L1 and the main skeleton of a unit adjacent to L1 or L2, or may be formed by side chains bonded to the main skeleton of a single ring or fused ring constituting the aromatic group in L1 or L2.

[0181] When the aromatic group in L1 or L2 contains an element capable of non-covalent interaction with an element in an adjacent unit, a non-covalent bridge is formed between the element and the adjacent unit. In other words, the planarity of the main skeleton (i.e., the π plane) of the monocyclic or fused ring constituting the aromatic group in L1 or L2 is easily maintained, the association state of the compound is appropriately controlled, and the DOS broadening is narrowed, thereby reducing the dark current in the photoelectric conversion element.

[0182] (Specific examples of L1 and L2) Specific examples of L1 and L2 include groups represented by the following formulae. In each formula, the dotted line represents a bond to the adjacent unit; for example, when the formula below is L1, it represents a bond to A1, L1, or D1, and when the formula below is L2, it represents a bond to D2, L2, or A2. "**" represents a bond to the chemical structure shown on the left side of each formula. In the formula, R L1 When there are multiple R groups, they may be the same or different. L1 exists and R L1 When multiple examples of R are listed, any of the R in the chemical structure shown on the left side of each example may be used. L1 But R L1 There is no particular limitation on which of the above examples is used, and all combinations are included as preferred embodiments.

[0183] [ka]

[0184] [m and n] In formula (1), m and n each independently represent an integer of 1 to 3. m and n each independently represent preferably 1 or 2, and more preferably 1.

[0185] When m is 2 or 3, (L1) mThe plurality of L1s in n may be the same or different. From the viewpoint of ease of compound synthesis, it is preferable that they are the same. Similarly, when n is 2 or 3, the plurality of L2s in

[0186] <A1 and A2; acceptor> In formula (1), A1 and A2 are each independently an electron-withdrawing monovalent group having at least one aromatic ring. The chemical structures of A1 and A2 may be the same as or different from each other. From the viewpoint of ease of compound synthesis, it is preferable that the chemical structures of A1 and A2 are the same.

[0187] A1 and A2 are each preferably a group represented by the following formula (A-1). In formula (A-1), the dotted line represents a bond with (L1) in formula (1) m or a bond with (L2) n and indicates a bond with.

[0188]

Chemical formula

[0189] In formula (A-1), Ar represents a carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.

[0190] The carbocyclic ring may be an aromatic carbocyclic ring. Specific examples of the aromatic carbocyclic ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. Preferably, they are a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.

[0191] The heterocycle may be an aromatic heterocycle. Specific examples of aromatic heterocycles include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0192] Examples of the substituent that the carbocycle and heterocycle may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, a nitro group, a cyano group, and a monovalent heterocyclic group, and are preferably a fluorine atom, a chlorine atom, an alkyloxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a nitro group, or a cyano group, and more preferably a fluorine atom, a chlorine atom, a nitro group, or a cyano group.

[0193] [Chemical structures of A1 and A2] In formula (1), A1 and A2 are preferably each independently any of the groups represented by the following formulae (a-1) to (a-8). In each formula, the symbol "*" indicates (L1) in formula (1). m Bond with or (L2) n This shows the bond between .

[0194] [ka]

[0195] In formulas (a-1) to (a-8), R a1 ~R a6 are each independently a hydrogen atom, a halogen atom, or a cyano group. From the viewpoint that the compound is likely to absorb light of a long wavelength, R a1 ~R a6 are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, or a cyano group, more preferably a cyano group. From the viewpoint that the compound easily absorbs light of a long wavelength, A1 and A2 are each independently preferably any of the groups represented by formula (a-1) or formula (a-4) to formula (a-8), more preferably any of the groups represented by formula (a-1), formula (a-4), or formula (a-5), and even more preferably a group represented by formula (a-1) or formula (a-5).

[0196] (Specific examples of A1 and A2) Specific examples of A1 and A2 include groups represented by the following formulae: In each formula, the symbol "*" represents (L1) in formula (1). m Bond with or (L2) n This shows the bond between .

[0197] [ka]

[0198] <Specific Examples of Compounds of the Present Disclosure> In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. The compounds of the present disclosure are represented by formula (1): D1 and D2 are each independently any group represented by formula (D-1) to formula (D-7), L1 and L2 are each independently any group represented by formula (L1-1) to formula (L1-9), m and n are each independently an integer of 1 to 3; It is preferable that A1 and A2 are groups represented by formula (A-1).

[0199] The compounds of the present disclosure are represented by formula (1): D1 and D2 are each independently a group represented by formula (d-1-1), formula (d-2-3), formula (d-4-1), or formula (d-4-2), L1 and L2 are each independently a group represented by any one of formulas (L1-1) to (L1-4), and have a side chain containing an element capable of non-covalently interacting with an element in an adjacent unit; m and n are 1, It is more preferable that A1 and A2 are each independently any of the groups represented by formulae (a-1) to (a-8).

[0200] More specific examples of preferred compounds of the present disclosure include compounds represented by the following formulas:

[0201] [ka]

[0202] [ka]

[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] [ka]

[0207] [ka]

[0208] ≪Composition≫ The composition of the present disclosure contains a p-type semiconductor material and an n-type semiconductor material, and preferably contains the compound of the present disclosure as the n-type semiconductor material.

[0209] The composition of the present disclosure may contain components other than p-type semiconductor materials and n-type semiconductor materials. Further, the composition of the present disclosure may contain only the compounds of the present disclosure as the n-type semiconductor material, or may contain other compounds other than the compounds of the present disclosure. Other compounds that may be included as the n-type semiconductor material may be low molecular weight compounds or high molecular weight compounds.

[0210] <n-type semiconductor material> Examples of low molecular weight compounds that may be included as the n-type semiconductor material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and phenanthrene derivatives such as bathocuproine.

[0211] Examples of high molecular weight compounds that may be included as the n-type semiconductor material include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

[0212] Further, other compounds may be fullerene derivatives.

[0213] Here, the fullerene derivative refers to fullerene (C 60 Fullerene, C 70 Fullerene, C ... (the text seems to be incomplete here with repeated "Fullerene, C" lines without a clear pattern to continue the full translation for the rest of the text related to fullerene derivatives. Please check and provide the complete text if possible). 76 Fullerene, C 78 Fullerene, and C 84It refers to a compound in which at least a part of (fullerene) is modified. In other words, it refers to a compound having one or more groups attached to the fullerene skeleton. Hereinafter, particularly C 60 The fullerene derivative of fullerene is referred to as "C 60 fullerene derivative", and C 70 The fullerene derivative of fullerene may be referred to as "C 70 fullerene derivative".

[0214] The fullerene derivative that can be included as an n-type semiconductor material is not particularly limited as long as it does not impair the object of the present disclosure.

[0215] C that can be included as an n-type semiconductor material 60 Specific examples of the fullerene derivative include the following compounds.

[0216]

Chemical formula

[0217] In the formula of the above C 60 fullerene derivative, the definition of R is as described in paragraph number

[0203] of International Publication No. 2023 / 100844. When there are a plurality of Rs, the plurality of Rs may be the same as or different from each other.

[0218] C 70 Examples of the fullerene derivative include the following compounds.

[0219]

Chemical formula

[0220] <p-type semiconductor material> The p-type semiconductor material is preferably a polymer compound having a predetermined weight average molecular weight in terms of polystyrene.

[0221] Here, the weight average molecular weight in terms of polystyrene refers to a weight average molecular weight calculated using gel permeation chromatography (GPC) and a polystyrene standard sample.

[0222] The weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in solvents.

[0223] The p-type semiconductor material is preferably a π-conjugated polymer compound (also called a DA-type conjugated polymer compound) containing a donor structural unit (also called a D structural unit) and an acceptor structural unit (also called an A structural unit).Which is the donor structural unit or the acceptor structural unit can be determined relatively from the HOMO or LUMO energy level.

[0224] Here, a donor building block is a building block that has an excess of π electrons, and an acceptor building block is a building block that has a deficiency of π electrons.

[0225] In the present disclosure, structural units that can constitute a p-type semiconductor material include structural units in which a donor structural unit and an acceptor structural unit are directly bonded, as well as structural units in which a donor structural unit and an acceptor structural unit are bonded via any suitable spacer (group or structural unit).

[0226] Examples of p-type semiconductor materials that are polymer compounds include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, and polyfluorene and derivatives thereof.

[0227] The p-type semiconductor material is preferably a polymer compound containing at least one selected from the group consisting of a constitutional unit represented by the following formula (3) and a constitutional unit represented by the following formula (4). The constitutional unit represented by the following formula (3) is usually preferably a donor constitutional unit. The constitutional unit represented by the following formula (4) is usually preferably an acceptor constitutional unit.

[0228] [ka]

[0229] -Formula (3)- In formula (3), Ar 3 and Ar 4 each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7).

[0230] [ka]

[0231] In formulas (Z-1) to (Z-7), the definition of each R is independently the same as the definition of "side chain A" in the present disclosure. In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different.

[0232] Ar 3 and Ar 4 The aromatic heterocycle that can constitute the above ring includes not only a single ring and a fused ring in which the heterocycle itself exhibits aromaticity, but also a ring in which an aromatic ring is fused to a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0233] Ar 3 and Ar 4The aromatic heterocycles that can constitute the above may each be a single ring or a fused ring. When the aromatic heterocycle is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the rings may be fused rings having aromaticity. When these rings have multiple substituents, these substituents may be the same or different.

[0234] Ar 3 and Ar 4 Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0235] Specific examples of the aromatic heterocycle include the ring structures of the compounds already described as aromatic heterocyclic compounds, such as an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0236] The constitutional unit represented by formula (3) is preferably a constitutional unit represented by the following formula (3-1), (3-2) or (3-3).

[0237] [ka]

[0238] In formulas (3-1), (3-2) and (3-3), Ar 3 , Ar 4 The definitions of and R are respectively defined as Ar in formula (3). 3, Ar 4 and the definition of "side chain A" in this disclosure.

[0239] Specific examples of suitable structural units represented by formula (3) include structural units represented by the following formulas.

[0240] [ka]

[0241] In the above formula, the definition of R is the same as the definition of "side chain A" in the present disclosure. When there are two R's, the two R's may be the same or different.

[0242] More specific examples of preferred structural units represented by formula (3) include structural units represented by the following formulas.

[0243] [ka]

[0244] -Formula (4)- In formula (4), Ar 5 represents a divalent aromatic heterocyclic group.

[0245] Ar 5 The divalent aromatic heterocyclic group represented by the following formula (I) preferably has 2 to 60 carbon atoms, more preferably 4 to 60 carbon atoms, and even more preferably 4 to 20 carbon atoms.

[0246] Ar 5 The divalent aromatic heterocyclic group represented by the formula (Ar) may have a substituent. 5Examples of the substituent that the divalent aromatic heterocyclic group represented by the formula (I) may have include a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amide group, an optionally substituted acid imide group, an optionally substituted substituted oxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a cyano group, and a nitro group.

[0247] As the constitutional unit represented by formula (4), constitutional units represented by the following formulae (4-1) to (4-10) are preferred.

[0248] [ka]

[0249] In formulas (4-1) to (4-10), R is defined as the "side chain A" in the present disclosure. X 2 and X 3 each independently represents an oxygen atom or a sulfur atom. Z 1 and Z 2 each independently represents a group represented by ═C(R)— or a nitrogen atom. When there are two R's, the two R's may be the same or different.

[0250] X in formulas (4-1) to (4-10) 2 and X 3 are preferably sulfur atoms from the viewpoint of availability of raw material compounds.

[0251] As described above, the structural units represented by formulae (4-1) to (4-10) can generally function as acceptor structural units. However, without being limited thereto, the structural units represented by formulae (4-4), (4-5), and (4-7) in particular can also function as donor structural units.

[0252] The p-type semiconductor material is preferably a π-conjugated polymer compound that includes a structural unit containing a thiophene skeleton and that includes a π-conjugated system.

[0253] Ar 5 Specific examples of the divalent aromatic heterocyclic group represented by the formula (101) to the formula (191) described in paragraphs

[0255] to

[0258] of WO 2023 / 100844. These groups may further have a substituent.

[0254] The polymer compound that is a p-type semiconductor material is preferably a π-conjugated polymer compound that includes a constitutional unit represented by formula (3) as a donor constitutional unit and a constitutional unit represented by formula (4) as an acceptor constitutional unit.

[0255] In a polymer compound that is a p-type semiconductor material, the polymer compound that is a p-type semiconductor material may contain, as a structural unit, a structure in which the structural unit represented by formula (3) and the structural unit represented by formula (4) already explained are linked together.

[0256] The polymer compound that is a p-type semiconductor material may contain two or more types of constitutional units represented by formula (3), or may contain two or more types of constitutional units represented by formula (4).

[0257] For example, from the viewpoint of improving solubility in a solvent, the polymer compound that is a p-type semiconductor material may contain a constitutional unit represented by formula (IV) described in paragraphs

[0263] to

[0277] of WO 2023 / 100844.

[0258] The constitutional unit represented by formula (IV) is preferably a constitutional unit represented by the following formula (IV-1) or formula (IV-2).

[0259] [ka]

[0260] In formula (IV-1) and formula (IV-2), the definition of R is the same as the definition of "side chain A" in the present disclosure. The two R may be the same or different.

[0261] The structural unit constituting the polymer compound that is a p-type semiconductor material may be a structural unit in which two or more structural units selected from the above structural units are combined and linked together.

[0262] When a polymer compound serving as a p-type semiconductor material contains a constitutional unit represented by formula (3) and / or a constitutional unit represented by formula (4), the total amount of the constitutional unit represented by formula (3) and the constitutional unit represented by formula (4) is usually preferably 20 mol % to 100 mol %, assuming the amount of all constitutional units contained in the polymer compound as 100 mol %. From the viewpoint of improving the charge transport properties as a p-type semiconductor material, it is more preferably 40 mol % to 100 mol %, and even more preferably 50 mol % to 100 mol %.

[0263] Specific examples of polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas (P-1) to (P-19).

[0264] [ka]

[0265] [ka]

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270] [ka]

[0271] In the above formula, the definition of R is the same as the definition of "side chain A" in the present disclosure. Multiple R may be the same or different.

[0272] When the polymer compound exemplified above is used as a p-type semiconductor material, it is possible to suppress a decrease in EQE due to heat treatment during a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device, or the like, or to further improve the EQE, thereby improving the heat resistance of the photoelectric conversion element.

[0273] Ink The ink of the present disclosure preferably contains the compound of the present disclosure and a solvent. The ink of the present disclosure also preferably contains the p-type semiconductor material, the n-type semiconductor material, and a solvent. Since the ink of the present disclosure contains the compound of the present disclosure as the n-type semiconductor material, it is preferably an ink for forming an active layer of a photoelectric conversion element, and more preferably an ink for forming a bulk heterojunction active layer.

[0274] According to the ink of the present disclosure, by containing a p-type semiconductor material and a compound of the present disclosure, it is possible to suppress a decrease in EQE or to further improve the EQE due to heat treatment during, for example, a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device, thereby improving heat resistance.

[0275] The solvent may be, for example, a mixed solvent that combines the first and second solvents described below. Specifically, when the ink contains two or more solvents, it preferably contains a main solvent (first solvent) that is the main component, and an additional solvent (second solvent) that is added to improve solubility, etc. The solvent may be the first solvent alone.

[0276] The first and second solvents and their combinations that can be suitably used in the ink for forming the active layer will be described below.

[0277] <First solvent> The first solvent is preferably a solvent in which the p-type semiconductor material can be dissolved, and is preferably an aromatic hydrocarbon.

[0278] Examples of aromatic hydrocarbons include toluene, xylenes (e.g., o-xylene, m-xylene, p-xylene), chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, trimethylbenzenes (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzenes (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalenes (e.g., 1-methylnaphthalene), 1-chloronaphthalene, bromobenzene, tetralin, and indane.

[0279] The first solvent may be composed of one type of aromatic hydrocarbon or two or more types of aromatic hydrocarbons, but is preferably composed of one type of aromatic hydrocarbon.

[0280] The first solvent is preferably one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, and indan, and more preferably toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, mesitylene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, or indan.

[0281] <Second solvent> The second solvent is preferably selected from the viewpoint of facilitating the production process and further improving the properties of the photoelectric conversion element. Examples of the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone; ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate, and benzyl benzoate; ether solvents such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and 1-methoxynaphthalene; 1,2,4-trimethylbenzene, 1,2,4-trichlorobenzene, tetralin, 2-isopropylphenol, 2-isopropyl-5-methylanisole, and bromobenzene.

[0282] The second solvent is preferably, for example, acetophenone, propiophenone, butyl benzoate, or methyl benzoate from the viewpoint of increasing wavelength.

[0283] <Combination of first and second solvents> Examples of suitable combinations of the first solvent and the second solvent include combinations of tetralin and ethyl benzoate, tetralin and propyl benzoate, tetralin and butyl benzoate, o-dichlorobenzene and 1,2-dimethoxybenzene, and o-dichlorobenzene and methyl benzoate, and more preferably combinations of tetralin and butyl benzoate, and o-dichlorobenzene and 1,2-dimethoxybenzene.

[0284] <Mass ratio of first solvent to second solvent> The mass ratio of the first solvent, which is the main solvent, to the second solvent, which is the additive solvent (first solvent:second solvent), is preferably in the range of 50:50 to 99:1, from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material.

[0285] <any other solvent> The solvent may contain any other solvent in addition to the first and second solvents. When the total mass of all solvents contained in the ink is taken as 100 mass%, the content of the other solvent is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less. The other solvent is preferably a solvent with a boiling point higher than that of the second solvent.

[0286] In addition to the first solvent, the second solvent, the p-type semiconductor material, and the n-type semiconductor material, the ink may contain optional components such as a surfactant, an ultraviolet absorber, an antioxidant, a sensitizer for increasing the function of generating charges by absorbed light, and a light stabilizer for increasing stability against ultraviolet light, to the extent that the objects and effects of the present disclosure are not impaired.

[0287] The concentrations of the p-type semiconductor material and the n-type semiconductor material in the ink can be set to any suitable concentration within a range that does not impair the object of the present disclosure, taking into consideration factors such as solubility in the solvent.

[0288] The mass ratio of the "p-type semiconductor material" to the "n-type semiconductor material" in the ink is usually preferably in the range of 1 / 0.1 to 1 / 10, more preferably in the range of 1 / 0.5 to 1 / 2, and even more preferably 1 / 1.5.

[0289] The total content of the "p-type semiconductor material" and "n-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.25% by mass or more. The total content of the "p-type semiconductor material" and "n-type semiconductor material" in the ink is usually preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 7.50% by mass or less.

[0290] The content of the "p-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.10% by mass or more. The content of the "p-type semiconductor material" in the ink is usually preferably 10% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less.

[0291] The content of the "n-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.15% by mass or more. The content of the "n-type semiconductor material" in the ink is usually preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 4.50% by mass or less.

[0292] The ink can be prepared by a known method, for example, by mixing a first solvent or a first solvent and a second solvent to prepare a mixed solvent, and then adding a p-type semiconductor material and an n-type semiconductor material to the resulting mixed solvent, or by adding a p-type semiconductor material to the first solvent, adding an n-type semiconductor material to the second solvent, and then mixing the first solvent and the second solvent to which each material has been added.

[0293] The first and second solvents and the p-type and n-type semiconductor materials may be mixed by heating to a temperature equal to or lower than the boiling point of the solvent.

[0294] After mixing the first and second solvents with the p-type and n-type semiconductor materials, the resulting mixture may be filtered using a filter, and the resulting filtrate may be used as a filtrate. The filter may be, for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE).

[0295] <Photoelectric conversion element> The photoelectric conversion element of the present disclosure includes an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material, and the n-type semiconductor material preferably includes the compound of the present disclosure. Preferred aspects of the p-type semiconductor material and the n-type semiconductor material are as described above.

[0296] According to the photoelectric conversion element of the present disclosure, by having the above-mentioned configuration, it is possible to suppress a decrease in external quantum efficiency due to heat treatment during the manufacturing process of the photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, and to effectively improve heat resistance.

[0297] Here, an example of a configuration that the photoelectric conversion element of the present disclosure can take will be described. Figure 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure.

[0298] 1, a photoelectric conversion element 10 is provided on a support substrate 11. The photoelectric conversion element 10 includes an anode 12 provided in contact with the support substrate 11, a hole transport layer 13 provided in contact with the anode 12, an active layer 14 provided in contact with the hole transport layer 13, an electron transport layer 15 provided in contact with the active layer 14, and a cathode 16 provided in contact with the electron transport layer 15. In this configuration example, a sealing member 17 is further provided in contact with the cathode 16.

[0299] Another example of a photoelectric conversion element includes a cathode provided in contact with a support substrate, an electron transport layer provided in contact with the cathode, an active layer provided in contact with the electron transport layer, a hole transport layer provided in contact with the active layer, and an anode provided in contact with the hole transport layer. In this example, a sealing member is further provided in contact with the anode.

[0300] Components that can be included in the photoelectric conversion element of the present disclosure will be specifically described below.

[0301] <Substrate> A photoelectric conversion element is usually formed on a substrate (support substrate). It may also be sealed with a further substrate (sealing substrate). One of a pair of electrodes, consisting of an anode and a cathode, is usually formed on the substrate. The material of the substrate is not particularly limited, as long as it is a material that is not chemically changed, especially when a layer containing an organic compound is formed.

[0302] Examples of materials for the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the opposite side to the electrode provided on the opaque substrate side (in other words, the electrode on the side farther from the opaque substrate) be a transparent or semi-transparent electrode.

[0303] <Electrode> The photoelectric conversion element includes a pair of electrodes, an anode and a cathode, at least one of which is preferably a transparent or semi-transparent electrode to allow light to enter.

[0304] Examples of transparent or semitransparent electrode materials include conductive metal oxide films and semitransparent metal thin films. Specific examples include conductive materials such as indium oxide, zinc oxide, tin oxide, and their composites, such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, as well as gold, platinum, silver, and copper. Preferred transparent or semitransparent electrode materials include ITO, IZO, and tin oxide. Alternatively, transparent conductive films made of organic compounds such as polyaniline and its derivatives, polythiophene and its derivatives, etc. may be used as electrodes. The transparent or semitransparent electrode may be an anode or a cathode.

[0305] As long as one electrode of a pair of electrodes is transparent or translucent, the other electrode may have low optical transparency. Examples of materials for electrodes with low optical transparency include metals and conductive polymers. Specific examples of materials for electrodes with low optical transparency include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, and ytterbium, alloys of two or more of these metals, alloys of one or more of these metals with one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, graphite, graphite intercalation compounds, polyaniline and its derivatives, and polythiophene and its derivatives. The alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

[0306] <Active layer> The active layer included in the photoelectric conversion element of the present disclosure is assumed to have a bulk heterojunction structure and includes a p-type semiconductor material and an n-type semiconductor material, and the active layer includes the compound of the present disclosure as the n-type semiconductor material.

[0307] The thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness taking into consideration the balance between suppressing dark current and extracting the generated photocurrent. In particular, from the viewpoint of further reducing dark current, the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more. In addition, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less.

[0308] <Middle class> As shown in FIG. 1, the photoelectric conversion element of the present disclosure preferably includes an intermediate layer (buffer layer) such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer) as a component for improving properties such as photoelectric conversion efficiency.

[0309] Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and a mixture (PEDOT:PSS) of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonate)).

[0310] As shown in Figure 1, the photoelectric conversion element preferably includes a hole transport layer between the anode and the active layer. The hole transport layer has the function of transporting holes from the active layer to the electrode.

[0311] The hole transport layer provided in contact with the anode may be particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the anode has the function of promoting the injection of holes into the anode. The hole transport layer (hole injection layer) may be in contact with the active layer.

[0312] The hole transport layer includes a hole transport material. Examples of the hole transport material include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO), and molybdenum oxide (MoO). Examples of hole transport material products include Avantama P-10 and P-21.

[0313] The intermediate layer can be formed by any suitable conventionally known forming method, such as a vacuum deposition method or a coating method similar to the method for forming the active layer.

[0314] The photoelectric conversion element of the present disclosure preferably has a configuration in which the intermediate layer is an electron transport layer, and the substrate (support substrate), anode, hole transport layer, active layer, electron transport layer, and cathode are laminated in this order so as to be in contact with each other.

[0315] As shown in Figure 1, the photoelectric conversion element of the present disclosure preferably includes an electron transport layer as an intermediate layer between the cathode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the cathode. The electron transport layer may be in contact with the cathode. The electron transport layer may be in contact with the active layer.

[0316] The electron transport layer provided in contact with the cathode is sometimes called an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the cathode has the function of promoting the injection of electrons generated in the active layer into the cathode.

[0317] The electron transport layer contains an electron transporting material, such as polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

[0318] Examples of polyalkyleneimines and derivatives thereof include polymers obtained by polymerizing one or more alkyleneimines having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, in particular alkyleneimines having 2 to 4 carbon atoms, by a conventional method, as well as polymers obtained by reacting these with various compounds to chemically modify them. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

[0319] Examples of polymer compounds containing a fluorene structure include poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9,9'-dioctylfluorene)] (PFN) and PFN-P2.

[0320] Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. Metal oxides containing zinc are preferred, with zinc oxide being particularly preferred. Examples of metal oxide products include Avantama's N-10, N-11, N-12, N-13, N-20X, and N-21X, and Infinity PV's ZnO, ZnO (2.8%), ZnO (5.6%), and Doped ZnO.

[0321] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0322] <Sealing member> The photoelectric conversion element of the present disclosure preferably further includes a sealing member and is sealed with such a sealing member to form a sealed body. Any suitable conventionally known member can be used as the sealing member, and an example of the sealing member is a combination of a glass substrate (sealing substrate) and a sealing material (adhesive) such as a UV-curable resin.

[0323] The sealing member may be a sealing layer having a structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0324] The sealing layer is preferably formed from a material that has a moisture-blocking property (water vapor barrier property) or an oxygen-blocking property (oxygen barrier property). Suitable examples of materials for the sealing layer include organic materials such as trifluoropolyethylene, polytrifluorochloroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

[0325] The sealing member is generally made of a material that can withstand the heat treatment that is carried out when the photoelectric conversion element is incorporated into a device, for example, the application example described below.

[0326] <Applications of photoelectric conversion elements> The photoelectric conversion element of the present disclosure may be used as a photodetector element or a solar cell. The photoelectric conversion element of the present disclosure may be used immediately after production, or may be left to stand or stored after production and then used. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from the transparent or semitransparent electrode side while a voltage (reverse bias voltage) is applied between the electrodes, and can function as a photodetector (photosensor). Furthermore, by integrating a plurality of photodetectors, the element can also be used as an image sensor. Thus, the photoelectric conversion element of the present disclosure can be particularly suitably used as a photodetector.

[0327] Furthermore, the photoelectric conversion element of the present disclosure can generate photovoltaic power between the electrodes when irradiated with light, and can operate as a solar cell. A solar cell module can also be formed by integrating a plurality of photoelectric conversion elements.

[0328] The photoelectric conversion element of the present disclosure can be suitably applied as a photodetector element to detectors provided in various electronic devices such as workstations, personal computers, mobile information terminals, access control systems, digital cameras, and medical equipment.

[0329] The photoelectric conversion element of the present disclosure can be suitably applied to the image detection units (e.g., image sensors such as X-ray sensors) for solid-state imaging devices such as X-ray imaging devices and CMOS image sensors, detection units (e.g., near-infrared sensors) of biometric information authentication devices that detect predetermined features of a part of a living body, such as fingerprint detection units, face detection units, vein detection units, and iris detection units, and detection units of optical biosensors such as pulse oximeters, which are included in the above-mentioned exemplary electronic devices.

[0330] The photoelectric conversion element of the present disclosure includes the compound of the present disclosure, and therefore operates at a longer wavelength than conventional elements.

[0331] <Method of manufacturing photoelectric conversion element> The method for manufacturing the photoelectric conversion element of the present disclosure is not particularly limited. The photoelectric conversion element of the present disclosure can be manufactured by combining a suitable forming method with materials selected for forming the components. Hereinafter, a method for manufacturing a photoelectric conversion element having a configuration in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are in contact with each other in this order will be described.

[0332] (Process of preparing the substrate) In this step, for example, a support substrate provided with an anode is prepared. Alternatively, a substrate provided with a conductive thin film formed from the electrode material already described can be purchased from the market, and the conductive thin film can be patterned to form an anode as needed, thereby preparing a support substrate provided with an anode. When an anode is formed on a support substrate, the method for forming the anode is not particularly limited. The anode can be formed on the structure where the anode is to be formed (e.g., support substrate, active layer, hole transport layer) by any suitable conventional method such as vacuum deposition, sputtering, ion plating, plating, or coating using the materials already described.

[0333] (Hole transport layer forming step) The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the anode. The method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable conventional coating method. The hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material for the hole transport layer and a solvent already described above, or by a vacuum deposition method.

[0334] (Active layer formation process) In the method for producing a photoelectric conversion element of the present disclosure, an active layer is formed on a hole transport layer. The active layer, which is a main component, can be formed by any suitable conventionally known formation process. The active layer is preferably produced by a coating method using an ink (coating liquid). Preferred embodiments of the ink are as described above. Steps (i) and (ii) included in the process for forming the active layer, which is a main component of the present disclosure, are described below.

[0335] Process (i) Any suitable coating method can be used as a method for applying the ink to a coating target, and examples of the coating method include slit coating, knife coating, spin coating, microgravure coating, gravure coating, bar coating, inkjet printing, nozzle coating, and capillary coating, more preferably slit coating, spin coating, capillary coating, and bar coating, and even more preferably slit coating or spin coating.

[0336] The ink for forming an active layer is applied to a target selected depending on the photoelectric conversion element and its manufacturing method. The ink for forming an active layer can be applied to a functional layer of the photoelectric conversion element, in which an active layer may be present, during the manufacturing process of the photoelectric conversion element. Therefore, the target to which the ink for forming an active layer is applied varies depending on the layer structure of the photoelectric conversion element to be manufactured and the order of layer formation. For example, if the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are stacked, and the layer listed on the left is formed first, the target to which the ink for forming an active layer is applied will be the hole transport layer. Furthermore, for example, if the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are stacked, and the layer listed on the left is formed first, the target to which the ink for forming an active layer is applied will be the electron transport layer.

[0337] Process (ii) Any suitable method can be used to remove the solvent from the ink coating, i.e., to remove the solvent from the coating and solidify it. Examples of the method for removing the solvent include a method of directly heating using a hot plate in an inert gas atmosphere such as nitrogen gas, hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

[0338] The thickness of the active layer can be adjusted to any desired thickness by appropriately adjusting the solid content concentration in the coating solution and the conditions of step (i) and / or step (ii).

[0339] The step of forming the active layer may include other steps in addition to steps (i) and (ii) as long as the other steps do not impair the object and effect of the present disclosure. The method for manufacturing a photoelectric conversion element may be a method for manufacturing a photoelectric conversion element including a plurality of active layers, or may be a method in which steps (i) and (ii) are repeated multiple times.

[0340] The manufacturing method of the photoelectric conversion element of the present disclosure includes a step of forming an electron transport layer (electron injection layer) provided on the active layer. The method of forming the electron transport layer is not particularly limited. From the viewpoint of making the formation process of the electron transport layer simpler, it is preferable to form the electron transport layer by any conventionally known and suitable vacuum evaporation method.

[0341] (Step of forming the cathode) The method of forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by any conventionally known and suitable method such as a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, a plating method, etc. using the materials of the electrodes exemplified above. Through the above steps, the photoelectric conversion element of the present disclosure is manufactured.

[0342] (Step of forming the encapsulant) In forming the encapsulant, any conventionally known and suitable encapsulant (adhesive) and substrate (encapsulation substrate) are used. Specifically, after applying an encapsulant such as a UV curable resin on a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then bonding it without gaps with the encapsulant, the photoelectric conversion element is encapsulated in the gap between the support substrate and the encapsulation substrate using a method suitable for the selected encapsulant such as irradiation with UV light, whereby an encapsulant of the photoelectric conversion element can be obtained.

[0343] <Photo-detection element> The photoelectric conversion element of the present disclosure, particularly the photo-detection element (photo sensor), can be incorporated into an image sensor, a biometric authentication device (fingerprint authentication device, vein authentication device) and function as described above.

Examples

[0344] Hereinafter, examples are shown to explain the present disclosure in more detail. The present disclosure is not limited to the examples described below.

[0345] A photoelectric conversion element was fabricated using a p-type semiconductor material and an n-type semiconductor material.

[0346] <p-type semiconductor material> The polymer compound P-1 was synthesized by referring to the method described in International Publication No. WO 2011 / 052709. As the polymer compound P-19, PCE-10, manufactured by 1-material, was obtained from the market and used. As the polymer compound P-20, the following compound was used. The synthesis method will be described later.

[0347] (Polymer compound P-1)

[0348] [Chemical formula]

[0349] (Polymer compound P-19)

[0350] [Chemical formula]

[0351] (Polymer compound P-20)

[0352] [Chemical formula]

[0353] [n-type semiconductor material] As the n-type semiconductor material, the following compound was used. The synthesis method will be described later. The compound RN-3 was synthesized by referring to the method described in International Publication No. WO 2021 / 079140.

[0354] (Compound N-1)

[0355] [Chemical formula]

[0356] (Compound N-2)

[0357] [Chemical formula]

[0358] (Compound RN-1)

[0359] [ka]

[0360] (Compound RN-2)

[0361] [ka]

[0362] (Compound RN-3)

[0363] JPEG2026019675000062.jpg7281

[0364] (Synthesis of Compound N-1) Compound 2 was synthesized using compound 1.

[0365] [ka]

[0366] A four-neck flask was charged with compound 1: 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 4.50 g) and DMF (11 g). After nitrogen purging, the flask was cooled to -20 to -30 °C. NBS (1.97 g) dissolved in DMF (11 g) was added dropwise, and the temperature was raised to 0 °C. After stirring for 1 hour, the reaction was quenched by adding aqueous sodium sulfite, and the temperature was raised to room temperature. Heptane and water were added, and the organic layer was extracted. The extract was washed twice with water, dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane) to obtain 4.7 g of crude compound 2 as a pale yellow liquid.

[0367] Compound 3 was synthesized using compound 1.

[0368] [ka]

[0369] A 100 mL four-neck flask was charged with compound 1:4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 4.00 g) and THF (45 mL). The flask was purged with nitrogen and then cooled to -73 °C. nBuLi (1.56 mol / L in hexane, 7.0 mL) was added and the internal temperature was maintained at -65 °C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.77 mL) and THF (23 mL) were added to a dropping funnel and added dropwise to the reaction mass at an internal temperature of -65 °C. After the addition was complete, the internal temperature was maintained at -65 °C for 1 hour, then the temperature was raised to room temperature and the mixture was stirred for 1 hour. After quenching by pouring in 20% aqueous ammonium chloride solution (5.3 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then totally concentrated using a rotary evaporator to obtain 5.4 g of crude compound 3.

[0370] Compound 4 was synthesized using compound 2 and compound 3.

[0371] [ka]

[0372] A three-neck flask was charged with 2.14 g of crude compound 2, 2.15 g of crude compound 3, and 18 g of THF, followed by 30 minutes of nitrogen bubbling. Pd(dba) (0.175 g, 0.19 mmol), P(tBu)HBF (0.111 g, 0.38 mmol), and 3 mol / L KPO aqueous solution (7.1 g) were added, in that order, and the mixture was heated to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (eluent: heptane) and then purified by recycled preparative GPC (chloroform solvent) to obtain 1.67 g of compound 4 as a red viscous liquid. The NMR spectrum of the resulting compound 4 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ7.12 (d, 2H), 6.93 (2H), 1.87(8H), 0.91-1.02(32H), 0.58-0.78(28H)

[0373] [ka]

[0374] A flask was charged with compound 4 (0.836 g, 1.04 mmol), Bpin2 (0.660 g, 2.6 mmol), [Ir(OMe)(cod)]2 (8 mg, 0.01 mmol), and tBu-bpy (7 mg, 0.02 mmol). After purging with nitrogen, 13 g of cyclohexane was added and the mixture was placed in an oil bath heated to 60 °C. After stirring for 1 hour, the mixture was removed from the oil bath and allowed to cool to room temperature. The cooled mass was quenched by pouring it into water. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered through a Kiriyama funnel loaded with 5 mm of silica gel, and then completely concentrated using a rotary evaporator to obtain 0.74 g of compound 5 as a red viscous liquid. 1H-NMR (300 MHz, CHLOROFORM-D) δ 7.43 (2H), 7.01 (2H), 1.87(8H), 1.35 (24H), 0.91-1.02 (32H), 0.58-0.78 (28H)

[0375] Compound 6 was synthesized using compound 5.

[0376] [ka]

[0377] A three-neck flask was charged with 0.55 g of compound 5 and 7 g of THF, and nitrogen was bubbled through for 30 minutes. Pd2(dba)3 (0.032 g), P(tBu3)HBF4 (0.02 g), and 3 mol / L K3PO4 aqueous solution (1.3 g) were added, in that order, and the mixture was heated to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated using a rotary evaporator. The resulting crude product was dissolved in heptane, washed three times with acetonitrile, and then concentrated. The resulting crude product was purified using a silica gel column (developing solvent: heptane) to obtain 0.51 g of compound 6 as a reddish-purple viscous liquid. The NMR spectrum of the resulting compound 6 was analyzed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.74 (2H), 7.47 (2H), 7.31 (2H), 7.02 (2H), 4.10 (4H), 1.83-1.92 (8H), 0.93-1.65 (62H), 0.62-0.74 (28H)

[0378] Compound 6 was used to synthesize compound N-1.

[0379] [ka]

[0380] A 50 mL four-neck flask was charged with compound 6 (0.518 g, 0.40 mmol), compound 7 (0.296 g, 1.21 mmol), p-TsOH·HO (0.231 g, 1.21 mmol), EtOH (4.7 g), toluene (10.4 g), and MgSO (0.26 g) and kept warm in an oil bath heated to 65 °C. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated using an evaporator and repulped with methanol to obtain a crude product. The resulting crude product was purified using a silica gel column (eluent: chloroform = 100 wt%) to obtain 0.612 g of compound N-1 as a black solid. The NMR spectrum of the resulting compound N-1 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.96 (2H) , 8.73 (2H), 8.12 (2H), 7.73 (2H), 7.39 (2H), 7.18 (2H), 4.19 (d, 4H), 1.88-2.05 (m, 10H), 1.52-1.70 (m, 8H), 1.40-1.44 (m, 8H), 0.95-1.06 (m, 44H), 0.64-0.78 (m, 28H)

[0381] (Synthesis of Compound N-2) Compound 9 was synthesized using compound 8.

[0382] [ka]

[0383] A 300 mL four-neck flask was charged with 3-Methoxythiophene (Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-Hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH·HO (0.833 g, 4.38 mmol), and toluene (100 g). The atmosphere was replaced with nitrogen and the mixture was heated to 110 °C. After stirring for 23 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (eluent: hexane = 100 wt%) to obtain 13.4 g of compound 9 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 9 was analyzed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.21 (1H), 3.81 (2H), 1.77-1.71 (1H), 1.46-1.28 (m, 24H), 0.90-0.86 (m, 6H)

[0384] Compound 10 was synthesized using compound 9.

[0385] [ka]

[0386] A 1 L four-neck flask was charged with compound 9 (15.35 g, 47.3 mmol) and THF (460.5 g). The flask was purged with nitrogen and then cooled to 0 °C. NBS (8.33 g, 46.8 mmol) was added and stirred at 0 °C. After stirring for 2 hours, 3% aqueous sodium sulfite solution (249 g) was added. The mixture was warmed to room temperature, and the aqueous layer was removed from the resulting mass by separation. The mixture was then dried over magnesium sulfate, filtered, and completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane) to obtain 18.53 g of compound 10 as a colorless liquid.

[0387] Compound 11 was synthesized using compound 10.

[0388] [ka]

[0389] A 3 L, four-neck flask was charged with compound 10 (92.28 g, 228.7 mmol) and THF (1038 mL). The flask was purged with nitrogen and then cooled to -73 °C. LDA (1 M in THF / Hexane, 228.7 mL, 228.7 mmol) was slowly added dropwise. After the addition was complete, the mixture was kept at an internal temperature of -73 °C for 2 hours. DMF (35.3 mL, 457.4 mmol) was slowly added dropwise to the reaction mass at an internal temperature of -73 °C. After the addition was complete, the mixture was warmed to room temperature and stirred for 2 hours. After quenching by adding 20% ​​aqueous ammonium chloride solution (489 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 70 / 1 (volume ratio)) to obtain 45.00 g of compound 11 as a yellow liquid. The NMR spectrum of the obtained compound 11 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.70 (1H), 7.37 (1H), 3.95 (2H), 1.80-1.72 (m, 1H), 1.57-1.27 (m, 24H), 0.90-0.86 (m, 6H)

[0390] Compound 12 was synthesized using compound 5 and compound 11.

[0391] [ka]

[0392] Compound 5 (0.99 g, 0.95 mmol), compound 11 (0.95 g, 2.2 mmol), and THF (14 g) were charged into a 50 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.044 g), P(tBu3)HBF4 (0.028 g), and 3 mol / L K3PO4 aqueous solution (1.8 g) were added in that order, and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated on a rotary evaporator. The resulting crude product was dissolved in heptane, washed three times with acetonitrile, and then concentrated. The resulting crude product was purified using a silica gel column (developing solvent: heptane) to obtain 0.53 g of compound 12 as a red-purple viscous liquid. NMR spectroscopy of the resulting compound 12 was performed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.74 (2H), 7.46 (2H), 7.31 (2H), 7.02 (2H), 4.09 (4H), 1.83-1.97 (8H), 0.93-1.65 (94H), 0.61-0.74 (m, 28H)

[0393] Compound 32 was synthesized according to the following scheme. The NMR spectrum of the obtained compound 32 was analyzed. The results are as follows. 1 H-NMR (300 MHz, DMSO―d6) δ 8.36(1H), 8.18(1H), 6.05(1H)

[0394] [ka]

[0395] Compound N-2 was synthesized using compound 12 and compound 32.

[0396] [ka]

[0397] A 100 mL four-neck flask was charged with compound 12 (0.360 g, 0.239 mmol), compound a (0.377 g), pTsOH·HO (0.319 g), EtOH (23.4 g), and toluene (9.7 g). The mixture was then placed in an oil bath heated to 65°C and kept at this temperature for 2 hours. The mixture was then removed from the oil bath and allowed to cool to room temperature. It was then filtered, washed with methanol, ethanol, and heptane, and dried to obtain a crude product. Purification by recycled preparative GPC (chloroform solvent) yielded 178 mg of compound N-2 as a black solid. The NMR spectrum of the resulting compound N-2 was analyzed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.82 (2H), 8.46 (2H), 8.39 (2H), 7.76 (2H), 7.34 (2H), 7.18 (2H), 4.20 (4H), 1.99 (8H), 0.66-1.65 (122H)

[0398] (Synthesis of compound RN-1) Compound 13 was synthesized using compound 9.

[0399] [ka]

[0400] A 200 mL four-neck flask was charged with compound 9 (4.0 g, 12.3 mmol) and THF (45 mL), purged with nitrogen, and then cooled to -73°C. LDA (1 M in THF / Hexane, 13.6 mL, 13.6 mmol) was charged and the internal temperature was maintained at -65°C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.2 mL, 18.5 mmol) and THF (22.5 mL) were charged into a dropping funnel and added dropwise to the reaction mass at an internal temperature of -65°C. After the addition was complete, the internal temperature was maintained at -65°C for 1 hour, then the temperature was raised to room temperature and the mixture was stirred for 2 hours. After quenching by pouring in 20% aqueous ammonium chloride solution (26 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 5.91 g of compound 13 as a crude product. The NMR spectrum of the resulting compound 13 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.26 (1H), 6.56 (1H), 3.82 (2H), 1.74-1.72 (1H), 1.57-1.19 (m, 36H), 00.88 (6H)

[0401] Compound 14 was synthesized using compound 13.

[0402] [ka]

[0403] Crude compound 13 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (JiangSu GR-Chem Co., Ltd.), and THF (149 mL) were charged into a 500 mL four-neck flask and nitrogen was bubbled through for 30 minutes. Pd2(dba)3 (0.600 g, 0.655 mmol), P(tBu3)HBF4 (0.399 g, 1.38 mmol), and 3 mol / L K3PO4 aqueous solution (60.6 g) were added in that order and the temperature was raised to 65 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 3.72 g of compound 14 as a yellow-brown liquid. The NMR spectrum of the obtained compound 14 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.08 (1H), 6.29 (1H), 4.06 (2H), 3.83 (2H), 1.85-1.27 (m, 34H), 0.98-0.86 (m, 12H)

[0404] Compound 15 was synthesized using compound 14.

[0405] [ka]

[0406] A 100 mL four-neck flask was charged with compound 14 (1.60 g, 2.84 mmol) and chloroform (56.0 g). The flask was purged with nitrogen and then cooled to 0°C. NBS (0.501 g, 2.81 mmol) was added and stirred at 0°C. After stirring for 2 hours, water (40.0 g) was added and the mixture was warmed to room temperature. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 1.84 g of compound 15 as a yellow-brown liquid. The NMR spectrum of the resulting compound 15 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (1H), 7.45 (1H), 7.02 (1H), 4.07 (2H), 3.93 (2H), 1.86-1.27 (m, 34H), 0.99-0.86 (m, 12H)

[0407] Compound 18 was synthesized using compound 3 and compound 15.

[0408] [ka]

[0409] Crude compound 3 (1.49 g), compound 15 (2.05 g, 3.20 mmol), and THF (29.6 g) were charged into a 100 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.113 g, 0.123 mmol), P(tBu3)HBF4 (0.0749 g, 0.258 mmol), and 3 mol / L K3PO4 aqueous solution (11.4 g) were added in that order and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated on a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 1.27 g of compound 18 as a red liquid. The NMR spectrum of the obtained compound 18 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.20 (1H), 7.13-7.10 (m, 2H), 6.93-6.91 (m, 1H), 4.10 (2H), 4.05 (2H), 1.93-0.57 (m, 80H)

[0410] Compound 19 was synthesized using compound 18.

[0411] [ka]

[0412] A 50 mL four-neck flask was charged with compound 18 (1.25 g, 1.30 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.497 g, 1.56 mmol) (JiangSu GR-Chem), Pd(OAc) (0.0364 g, 0.162 mmol), [(tBu)MePH]BF (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), KCO (0.538 g, 3.89 mmol), and DMF (12.5 g). Nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 120 °C and stirred for 5 hours. After cooling to room temperature, the mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.620 g of compound 19 as a deep red-purple liquid. The NMR spectrum of the resulting compound 19 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.74 (1H), 7.47 (2H), 7.32 (1H), 7.20 (1H), 7.12 (1H), 4.13 -4.06 (m, 6H), 1.89-0.60 (m, 95H)

[0413] Compound RN-1 was synthesized using compound 19.

[0414] [ka]

[0415] A 50 mL four-neck flask was charged with compound 19 (0.600 g, 0.499 mmol), compound b (0.366 g, 1.50 mmol), synthesized according to the method described in International Publication No. 2020 / 109823, p-TsOH·HO (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), and MgSO (0.300 g). The mixture was then placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated using an evaporator and repulped with methanol to obtain a crude product. The resulting crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.632 g (78% yield) of compound RN-1 as a black solid. The NMR spectrum of the resulting compound RN-1 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.98-8.95 (m, 2H), 8.76-8.72 (m, 2H), 8.14-8.11 (m, 2H), 7.74 (1H), 7.50-7.32 (m, 4H), 4.19 (6H), 2.06-0.64 (m, 95H)

[0416] (Synthesis of compound RN-2) Compound 27 was synthesized using compound 1.

[0417] [ka]

[0418] A 50 mL four-neck flask was charged with 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol), bis(pinacolato)diboron (1.58 g, 6.21 mmol), [Ir(OMe)(cod)]2 (19.8 mg, 0.0298 mmol), and tBu-bpy (16.0 mg, 0.0596 mmol). After purging with nitrogen, 15.0 g of cyclohexane was added and the flask was placed in an oil bath heated to 60 °C. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The cooled mass was quenched by pouring it into water. The aqueous layer was removed from the resulting mass by separation, then dried over magnesium sulfate, and filtered while passing through silica gel. The entire volume was then concentrated using a rotary evaporator to obtain 2.30 g of crude compound 27.

[0419] Compound 29 was synthesized using compound 27.

[0420] [ka]

[0421] A 50 mL three-neck flask was charged with compound 27 (0.775 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.870 g, 2.72 mmol), and THF (7.0 g), followed by 30 minutes of nitrogen bubbling. Pd2(dba)3 (0.054 g, 0.06 mmol), P(tBu3)HBF4 (0.034 g, 0.12 mmol), and 3 mol / L K3PO4 aqueous solution (2.19 g) were added in that order, and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated on a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 0 to 75 / 25 (mass ratio)) to obtain 0.521 g of compound 29 as a reddish-purple viscous liquid. The NMR spectrum of the obtained compound 29 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.47 (2H), 7.32 (2H), 4.11 (4H), 1.79-1.96 (m, 6H), 1.37-171 (m, 16H), 0.88-1.02(m, 28H), 0.60-0.73(m, 14H)

[0422] Compound RN-2 was synthesized using compound 29.

[0423] [ka]

[0424] A 50 mL four-neck flask was charged with compound 29 (0.521 g, 0.59 mmol), compound b (0.434 g, 1.78 mmol), p-TsOH·HO (0.338 g, 1.78 mmol), EtOH (4.7 g), toluene (10.4 g), and MgSO (0.26 g) and kept warm in an oil bath heated to 65 °C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated by evaporation and repulped with methanol to obtain a crude product. The resulting crude product was purified on a silica gel column (eluent: chloroform = 100 wt%) and then repulped with acetone to obtain 0.432 g (55% yield) of compound RN-2 as a blue-green-black solid. The NMR spectrum of the resulting compound RN-2 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.00 (2H), 8.79 (2H), 8.17 (2H), 7.73 (2H), 4.21 (4H), 1.89-2.08 (m, 6H), 1.40-1.73 (m, 16H), 0.95-1.06 (m, 28H), 0.64-0.74 (m, 14H)

[0425] (Synthesis of polymer compound P-20) Compound 46 was synthesized using compounds 44 and 45.

[0426] [ka]

[0427] Magnesium (1.61 g, 0.066 mol), THF (47 g), and iodine (32 mg) were added to a 1 L four-neck flask purged with nitrogen and stirred. After the purple color of the iodine disappeared, a solution of compound 45 (19.8 g, 0.063 mmol) in THF (36 g) was added dropwise to generate a Grignard reagent. A solution containing compound 44 (5.21 g, 0.025 mol), synthesized by the method described in WO 2011 / 136311, and THF (107 g) was added dropwise to the four-neck flask, ensuring that the internal temperature did not exceed 40°C. The reaction mixture was then stirred for 1 hour, and the reaction was quenched by adding aqueous ammonium chloride solution to the reaction mixture, followed by separation. The organic layer was dehydrated over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated on a rotary evaporator. The residue was purified by silica gel column chromatography (using hexane and ethyl acetate as the developing solvent) to obtain 14.21 g (20.7 mmol, yield 83%) of Compound 46.

[0428] Compound 46 1 The H-NMR measurement results are as follows: δ(ppm):7.82-7.76 (m, 1H), 7.64 (s, 2H), 7.43 (m, 2H), 7.31 (m, 10H), 7.25 (m, 2H), 7.21 (m, 1H), 7.13 (m, 2H), 6.91 (d, 1H), 6.64 (d, 1H), 6.43 (d, 1H), 3.72-3.64 (m, 1H), 2.63 (t, 4H), 1.61 (m, 4H), 1.22-1.34 (m, 12H), 0.86 (t, 6H)

[0429] Compound 47 was synthesized using compound 46.

[0430] [ka]

[0431] A 500 mL four-neck flask was charged with compound 46 (14.21 g, 0.0208 mmol) and heptane (130 g). The atmosphere in the reaction vessel was replaced with nitrogen, and trifluoroacetic acid (0.409 g, 0.0036 mmol) was added. The mixture was heated to 60 °C, stirred for 30 minutes, and then cooled to room temperature to obtain a reaction solution. The reaction solution was washed twice with water, and the organic layer was dehydrated with magnesium sulfate. The mixture was then passed through a Kiriyama funnel filled with silica gel. The filtrate was concentrated on a rotary evaporator to obtain 13.37 g of compound 47 (96.6% yield).

[0432] Compound 47 1 The H-NMR measurement results are as follows: δ(ppm):7.73 (s, 2H), 7.64 (s, 2H), 7.45-7.43 (m, 7H), 7.33-7.31 (m, 2H), 7.26 (s, 2H), 7.22 (s, 1H), 7.16-7.13 (m, 1H), 6.93 (d, 1H), 6.65 (d, 1H), 6.44 (d, 1H), 2.64 (t, 4H), 1.67-1.58 (m, 4H), 1.34-1.26 (m, 12H), 0.86 (t, 6H)

[0433] Compound 47 was used to synthesize compound 48.

[0434] [ka]

[0435] Compound 47 (25.0 g), tetraethylethylenediamine (5.6 mL), and dehydrated tetrahydrofuran (436 mL) were placed in an argon-purged flask and stirred to dissolve. The solution was then cooled to -65 °C in a cooling bath containing dry ice and acetone. A 1.6 mol / L nBuLi hexane solution (58.9 mL) was then added dropwise to the flask and stirred at -65 °C for 2 hours. While maintaining the temperature at -65 °C, a solution of triisopropoxyborane (19.74 g) in 40 mL of THF was added dropwise to the flask. The mixture was stirred at -65 °C for an additional hour, and then warmed to room temperature to obtain a reaction solution. Next, 290 mL of 2% hydrochloric acid was added to the reaction solution, and the mixture was separated. Magnesium sulfate and trimethylolethane (13.5 g) were added to the organic layer and stirred at room temperature for 1 hour. The magnesium sulfate was removed by filtration, and the filtrate was obtained. The solvent was removed from the filtrate under reduced pressure, toluene (700 mL) was added, and the precipitated solid was removed by filtration. Hexane was then added, and the supernatant was removed. The solvent was then removed under reduced pressure to obtain 37.7 g of compound 48 (yield 109%).

[0436] Compound 49 was synthesized using compound 44.

[0437] [ka]

[0438] Magnesium (12.37 g), THF (360 mL), and iodine (two grains) were added to an argon-purged flask and stirred. After the purple color of the iodine disappeared, a solution containing 1-bromo-3,5-diphenylbenzene (148.48 g) and THF (280 mL) was added dropwise to generate a Grignard reagent. A THF (820 mL) solution of compound 44 (35.88 g), synthesized by the method described in WO 2011 / 136311, was added dropwise so that the internal temperature did not exceed 40°C, yielding a reaction solution. The mixture was then stirred overnight, and the reaction was quenched by adding 10% aqueous ammonium chloride solution (450 mL) to the reaction solution, followed by separation. The organic layer was dehydrated over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated on a rotary evaporator. The residue was purified by silica gel column chromatography (using hexane and ethyl acetate as the developing solvent) to obtain 128.6 g of Compound 49 (yield 99%).

[0439] Compound 50 was synthesized using compound 49.

[0440] [ka]

[0441] Compound 49 (128.6 g) and toluene (1376 mL) were charged into an argon-purged flask. The atmosphere in the reaction vessel was purged with nitrogen, and then p-toluenesulfonic acid monohydrate (5.39 g) was added. The temperature was raised to 100 °C, stirred for 1.5 hours, and then cooled to room temperature to obtain a reaction solution. The reaction solution was washed with water, and the organic layer was dehydrated over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was concentrated on a rotary evaporator. Hexane (150 mL) was added to precipitate a solid, followed by the addition of toluene (50 mL) and hexane (50 mL). The mixture was then ice-cooled for 60 minutes, after which the precipitated solid was filtered and dried to obtain 106 g of compound 50 (96% yield).

[0442] Compound 51 was synthesized using compound 50.

[0443] [ka]

[0444] Compound 50 (28.38 g), tetraethylethylenediamine (6.5 mL), and 568 mL of anhydrous THF were placed in an argon-purged flask and stirred to dissolve. The solution was then cooled to -65 °C in a cooling bath containing dry ice and acetone, and a 1.6 mol / L nBuLi hexane solution (69.9 mL) was added dropwise and stirred at -65 °C for 1 hour. While maintaining the temperature at -65 °C, a solution of triisopropoxyborane (22.96 g) dissolved in 11.4 mL of THF was added dropwise, and the mixture was stirred at -65 °C for an additional 1 hour, after which the mixture was allowed to warm to room temperature. Next, 329 mL of 10% hydrochloric acid was added to the reaction mixture, and the mixture was separated. Magnesium sulfate and trimethylolethane (15.72 g) were added to the organic layer, and the mixture was stirred at room temperature for 1 hour. The magnesium sulfate was removed by filtration. The filtrate was evaporated under reduced pressure, chloroform (480 mL) was added, and the mixture was refrigerated overnight. The precipitated solid was removed, and the filtrate was evaporated under reduced pressure to give a crude product. The crude product was recrystallized from ethanol and hexane to give 36.18 g (yield 91.5%) of compound 51.

[0445] Compound 52 was synthesized according to the procedure described in the literature (Patent No. 6070722).

[0446] [ka]

[0447] Compound 48 (0.39 mmol), compound 51 (0.39 mmol), compound 52 (1.18 mmol), 4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole (0.40 mmol), 4,7-dibromo[1,2,5]thiadiazolo[3,4-c]pyridine (1.60 mmol), water (59.5 g), 40% by weight potassium phosphate aqueous solution (10.5 mL), THF (42 mL), tetralin (20 mL), and bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol) were added to a glass reaction vessel equipped with a cooling device at room temperature and stirred for 1 hour at 65 ° C. A mixture of phenylboronic acid (2 mmol) and a 40% by weight potassium phosphate aqueous solution (7.2 mL) was added to the reaction vessel and stirred for 1 hour at 65 ° C. The resulting organic layer was washed with an aqueous solution of sodium diethyldithiocarbamate, aqueous acetic acid, and water, and then added to methanol to collect the precipitated solid by filtration as a crude polymer. The resulting crude polymer was dissolved in tetralin and passed through 5B (JIS P 3801: 5 type B) filter paper, and then added to methanol again to collect the precipitated solid by filtration, yielding polymer compound P-20.

[0448] <Ink Preparation> [Preparation of Ink (I-1)] The following components were mixed and stirred for 8 hours at 60° C. The resulting mixture was filtered using a filter to obtain ink (I-1). P-type semiconductor material: polymer compound P-19...0.8% by mass N-type semiconductor material: Compound N-1...0.56% by mass n-type semiconductor material: C60PCBM...0.24 mass% Solvent: Chloroform / 1-chloronaphthalene = 97 wt% / 3 wt% ... remaining amount to make 100% by mass of the entire ink

[0449] C60PCBM ([6,6]-Phenyl C61 butyric acid methyl ester) was purchased from the market under the trade name "E100" manufactured by Frontier Carbon Corporation and used.

[0450] [Preparation of Inks (I-2) to (I-3)] Ink (I-2) or ink (I-3) was obtained in the same manner as in the preparation of ink (I-1), except that compound N-1 was changed to compound RN-1 or compound RN-2.

[0451] [Preparation of Ink (I-4)] The following components were mixed and stirred for 8 hours at 60° C. The resulting mixture was filtered using a filter to obtain ink (I-8). P-type semiconductor material: polymer compound P-20...2.6% by mass N-type semiconductor material: Compound N-2...2.6% by mass Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90 wt% / 10 wt% ... the remaining amount that makes up 100% of the total ink

[0452] [Preparation of Ink (I-5)] The following components were mixed, and the resulting mixture was filtered using a filter to obtain ink (I-5). ·P-type semiconductor material: Polymer compound P-1 …8.3mg / mL n-type semiconductor material: Compound RN-3...6.7mg / mL Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 95 vol% / 5 vol% ... the remaining amount to make the total ink 100 vol%

[0453] Example 1 [Production of photoelectric conversion element and its encapsulated body] A glass substrate on which a thin film (anode) of indium tin oxide (ITO) was formed to a thickness of 45 nm by sputtering was prepared, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

[0454] Next, the zinc oxide dispersion was applied to the cleaned glass substrate by spin coating to form a coating film, and then the substrate was placed on a hot plate and dried in the atmosphere at 120°C for 10 minutes to form an electron transport layer.

[0455] Next, ink (I-1) was applied onto the electron transport layer by spin coating to form a coating film, which was then dried by heating for 5 minutes on a hot plate heated to 70°C in air (pre-bake step), and then heated for 10 minutes on a hot plate at 100°C in a nitrogen atmosphere (post-bake step) to form an active layer. The thickness of the formed active layer was approximately 350 nm.

[0456] Next, a molybdenum oxide (MoO3) layer was formed on the formed active layer to a thickness of about 30 nm to serve as a hole transport layer.

[0457] Next, a silver (Ag) layer was formed on the formed hole transport layer to a thickness of about 60 nm to serve as a cathode. Through the above steps, a photoelectric conversion element was manufactured on the glass substrate.

[0458] Next, a UV-curable sealant was applied to the outer periphery of a glass substrate serving as a sealing substrate, and the glass substrate serving as a sealing substrate was attached to the center of the glass substrate serving as a support substrate. The glass substrate was then irradiated with UV light to seal the photodetector in the gap between the support substrate and the sealing substrate, thereby obtaining a sealed photoelectric conversion element. The photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate had a planar shape of 2 mm x 2 mm square when viewed from the thickness direction. The resulting sealed element was designated Sample 1.

[0459] [Photoelectric conversion element evaluation (dark current)] For the manufactured Sample 1, a voltage of -10 V to 2 V was applied to the sealed body of the photodetector in a dark state where no light was irradiated, and the current value when a reverse bias voltage of -3 V was applied, measured using a known method, was obtained as the dark current value. The results are shown in Table 1 below.

[0460] <Example 2, Comparative Example 1 and Comparative Example 2> Inks (I-2) to (I-4) were used instead of ink (I-1), and sealed photoelectric conversion elements were produced and evaluated in the same manner as in Example 1. The results are shown in Table 1 below. In the present disclosure, the dark current is defined as 5 μA / cm 2 The following is desirable:

[0461] <Comparative Example 3> A sealed photoelectric conversion element was produced and evaluated in the same manner as in Example 1, except that ink (I-5) was used instead of ink (I-1), ethoxylated polyethyleneimine (PEIE) was used as the electron transport layer, and ITO was used as the upper electrode. The results are shown in Table 1 below.

[0462] [Table 1]

[0463] As shown in Table 1, the photoelectric conversion element using the compound of the present disclosure as an n-type semiconductor material was able to reduce the dark current value to approximately 1 / 30 to 1 / 10 compared to a photoelectric conversion element using a conventional n-type semiconductor material. [Explanation of symbols]

[0464] 10 Photoelectric conversion element 11 Support substrate 12 Anode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Cathode 17 Sealing member

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), D1 and D2 each independently represent a polycyclic aromatic group having two bonds formed by condensing three or more monocyclic rings, wherein the conjugated structure connecting the two bonds in D1 and D2 via the shortest distance each independently contains four or more double bonds, and the number of single bonds in each monocyclic ring constituting the polycyclic aromatic group each independently is three or less; L1 and L2 each independently represent an aromatic group having two bonds, and each independently includes three or less double bonds in a conjugated structure connecting the two bonds in L1 and L2 at the shortest distance, and L1 and L2 may be the same or different, and are different from D1 and D2, m and n are each independently an integer of 1 to 3; A1 and A2 each independently represent an electron-withdrawing monovalent group having at least one aromatic ring.

2. The compound according to claim 1 , wherein D1 and D2 have the same main skeleton.

3. 3. The compound of claim 1 or claim 2, wherein D1 and D2 are donor groups.

4. The compound according to claim 1 or claim 2, wherein D1, D2, L1, and L2 have a thiophene structure.

5. 3. The compound according to claim 1, wherein D1 and D2 are polycyclic aromatic groups having five-membered fused rings.

6. The compound according to claim 1 or claim 2, wherein D1 and D2 do not contain an oxygen atom in the main skeleton.

7. The compound according to claim 1 or claim 2, wherein the polycyclic aromatic groups in D1 and D2 each independently have at least one of an sp3 carbon and an sp3 silicon, and a side chain is bonded to the sp3 carbon or sp3 silicon.

8. The compound according to claim 1 or 2, wherein D1 and D2 are each independently any of groups represented by the following formulas (D-1) to (D-7): 【Chemistry 2】 In formulas (D-1), (D-2), (D-6), and (D-7), X is a group represented by the following formula (X-1) or (X-2): 【Transformation 3】 In formulas (D-3) to (D-7), (X-1) and (X-2), R ｄ are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In formula (D-2), formula (D-5), and formula (D-7), Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ Either one of them may not be present.)

9. 3. The compound of claim 1 or claim 2, wherein m and n are 1.

10. 3. The compound according to claim 1, wherein the number of double bonds contained in the conjugated structure connecting the two bonds in L1 and L2 by the shortest distance is two or less.

11. The compound according to claim 1 or claim 2, wherein A1 and A2 are each independently any of groups represented by the following formulas (a-1) to (a-8): 【Chemistry 4】 (In formulas (a-1) to (a-8), R ａ１ ~R ａ６ are each independently a hydrogen atom, a halogen atom, or a cyano group.

12. A composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises the compound according to claim 1 or 2.

13. The composition according to claim 12, wherein the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): 【Transformation 5】 (In formula (3), Ar ３ and Ar ４ each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulas (Z-1) to (Z-7): 【Transformation 6】 In formulas (Z-1) to (Z-7), Each R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different, In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

14. An ink comprising the compound according to claim 1 or 2 and a solvent.

15. an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material; A photoelectric conversion element comprising the compound according to claim 1 or 2 as the n-type semiconductor material.

16. The photoelectric conversion element according to claim 15 , which is a photodetector element.

17. An optical sensor comprising the photoelectric conversion element according to claim 16.

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