Composition, photoelectric conversion element and optical sensor

Abstract

To provide: a composition capable of absorbing light having a long wavelength and suppressing a dark current in a photoelectric conversion element; a photoelectric conversion element; and an optical sensor.SOLUTION: A composition includes a p-type semiconductor material and an n-type semiconductor material. The p-type semiconductor material includes a structural unit X represented by the following formula and a structural unit Y that is a divalent group and that has a chemical structure different from that of the structural unit X. The LUMO energy of the p-type semiconductor material is -3.35 eV or more and -2.75 eV or less. The n-type semiconductor material is a compound represented by formula (n1). The absolute value of the difference between the HOMO energy of a compound Ia and the HOMO energy of a compound II, and the absolute value of the difference between the HOMO energy of a compound Ib and the HOMO energy of the compound II are both 2.75 eV or more and 3.90 eV or less. The structural unit X, the structural unit Y, the formula (n1), the compound Ia, and the compound II are as defined in the specification.SELECTED DRAWING: Figure 2

Description

[Technical Field]

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

[0002] 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 provided between the pair of electrodes. 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] As p-type organic semiconductors used in photoelectric conversion elements, for example, conjugated polymer compounds having a specific structure as described in Patent Document 1 are known. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-131716 Summary of the Invention [Problem to be solved by the invention]

[0005] Photoelectric conversion elements are used, for example, as photodetectors. Photoelectric conversion elements used as photodetectors are used with a voltage applied, and light incident on the element is converted and detected as a current. However, even when no light is incident, a weak current flows through the photoelectric conversion element. This current is known as dark current, and it can reduce the accuracy of light detection. On the other hand, knowledge about suppressing dark current in photoelectric conversion elements, and about photoelectric conversion using light with wavelengths in the SWIR (Short Wavelength Infrared) region, is currently limited.

[0006] The present disclosure has been made in view of the above, and relates to providing a composition that suppresses dark current in a photoelectric conversion element and is capable of absorbing light with a long wavelength, a photoelectric conversion element, and an optical sensor. [Means for solving the problem]

[0007] The present disclosure includes the following aspects. <1> comprising a p-type semiconductor material and an n-type semiconductor material, The p-type semiconductor material includes a structural unit X represented by the following formula and a structural unit Y which is a divalent group and has a chemical structure different from that of the structural unit X: the LUMO energy of the p-type semiconductor material is −3.35 eV or more and −2.75 eV or less;

[0008] [ka]

[0009] (In the structural unit X, Ar 1 and Ar 3 each independently represents an optionally substituted trivalent aromatic carbocyclic group or an optionally substituted trivalent aromatic heterocyclic group, Ar 2 each independently represent an optionally substituted tetravalent aromatic carbocyclic group or an optionally substituted tetravalent aromatic heterocyclic group, n is an integer from 0 to 3. The n-type semiconductor material is a compound represented by the following formula (n1): A 1 -PA 2 (n1) (In formula (n1), A 1 and A 2 are each independently an electron-withdrawing monovalent group, and P is a divalent group having a structure represented by the following formula (n2): Base A 1 The compound in which a hydrogen atom is bonded to the bond to the group P of the compound Ia is called compound Ia. 2The compound Ib is a compound in which a hydrogen atom is bonded to the bond to the group P. 1 and group A 2 wherein, when a compound II is a compound in which a hydrogen atom is bonded to each bond of the compound Ia and the compound II, the absolute value of the difference between the HOMO energy of the compound Ia and the HOMO energy of the compound II and the absolute value of the difference between the HOMO energy of the compound Ib and the HOMO energy of the compound II are both 2.75 eV or more and 3.90 eV or less.

[0010] [ka]

[0011] (In formula (n2), Ar 4 ~Ar 6 each independently represents a divalent aromatic carbocyclic group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent. <2> In the structural unit X, Ar 1 ~Ar 3 At least one of the groups is an aromatic heterocyclic group containing at least one of a sulfur atom and a nitrogen atom. <1> The composition described in <3> The structural unit X is a structure represented by the following formula (X1): <1> or <2> The composition described in

[0012] [ka]

[0013] (In formula (X1), n ​​is an integer of 0 to 3.) <4> Ar in formula (n2) 5 is a structure represented by the following formula (n3): <1> ~ <3> The composition according to any one of the preceding claims.

[0014] [ka]

[0015] (In formula (n3), X 2 represents a divalent group, Ar 7 and Ar 8 each independently represent an optionally substituted fused or non-fused trivalent aromatic carbocyclic group, or an optionally substituted fused or non-fused trivalent aromatic heterocyclic group, c and d are each independently 0 or 1. <5> 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 (I), a structural unit represented by the following formula (II), and a structural unit represented by the following formula (III): <1> ~ <4> The composition according to any one of the preceding claims.

[0016] [ka]

[0017] (In formula (I), Ar 9 and Ar 10 represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents a group represented by the following formulae (Z-1) to (Z-7).

[0018] [ka]

[0019] In formulas (Z-1) to (Z-7), R 1 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, cyano group, nitro group, -C(=O)-R Y or a group represented by -SO2-R Z represents a group represented by R Y and R Z are each independently hydrogen atoms, an alkyl group which may have a substituent, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted aryloxy group, or represents an optionally substituted monovalent heterocyclic group, R 1 If there are two, then two R 1 may be the same or different. In formula (II), Ar 11 represents an optionally substituted divalent monocyclic aromatic carbocyclic group or an optionally substituted divalent monocyclic aromatic heterocyclic group. In formula (III), Ar12 and Ar 13 each independently represents an aromatic carbocyclic group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and m represents an integer of 1 or greater. <6> It further contains a solvent and is an ink. <1> ~ <5> The composition according to any one of the preceding claims. <7> an anode, a cathode, and a cathode provided between the anode and the cathode; <1> ~ <5> and an active layer formed using the composition according to any one of the above items. <8> A photodetector element, <7> The photoelectric conversion element according to claim 1. <9> <7> or <8> An optical sensor comprising the photoelectric conversion element according to claim 1. [Effects of the Invention]

[0020] According to the present disclosure, a composition capable of suppressing dark current in a photoelectric conversion element and absorbing light with a long wavelength, a photoelectric conversion element, and an optical sensor are provided. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is an example of the ultraviolet-visible absorption spectrum of a p-type semiconductor material of the present disclosure. [Figure 2] FIG. 2 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element. DETAILED DESCRIPTION OF THE INVENTION

[0022] 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.

[0023] 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.

[0024] 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.

[0025] The following describes commonly used terms in this disclosure. In the description of this disclosure, the following descriptions apply unless otherwise specified.

[0026] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0027] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0028] "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 %.

[0029] 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.

[0030] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0031] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0032] 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, cyano group, nitro group, -C(=O)-R Y or a group represented by -SO2-R Z means a group represented by R Y and R Z are each independently hydrogen atoms, an alkyl group which may have a substituent, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent.

[0033] The embodiment of "optionally having a substituent" includes both a case where all hydrogen atoms constituting the compound or group are unsubstituted, and a case where one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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."

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] "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.

[0078] "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.

[0079] "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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] Examples of the substituted cycloalkynyl group include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0092] 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.

[0093] The symbol "*" that may be added to a chemical formula represents a bond. When a chemical formula contains two symbols "*", there is no particular limitation as to which of the two chemical structures each "*" represents a bond to.

[0094] "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.

[0095] The ink may be a solution or a dispersion such as an emulsion or suspension.

[0096] 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.

[0097] "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.

[0098] ≪Composition≫ The composition of the present disclosure comprises: comprising a p-type semiconductor material and an n-type semiconductor material, The p-type semiconductor material includes a structural unit X represented by the following formula and a structural unit Y which is a divalent group and has a chemical structure different from that of the structural unit X: The LUMO energy of the p-type semiconductor material is −3.35 eV or more and −2.75 eV or less.

[0099] [ka]

[0100] In the structural unit X, Ar 1 and Ar 3 each independently represents an optionally substituted trivalent aromatic carbocyclic group or an optionally substituted trivalent aromatic heterocyclic group, Ar 2 each independently represent an optionally substituted tetravalent aromatic carbocyclic group or an optionally substituted tetravalent aromatic heterocyclic group, n is an integer of 0 to 3. The n-type semiconductor material is a compound represented by the following formula (n1): A 1 -PA 2 (n1) (In formula (n1), A 1 and A 2 are each independently an electron-withdrawing monovalent group, and P is a divalent group having a structure represented by the following formula (n2): Base A 1 The compound in which a hydrogen atom is bonded to the bond to the group P of the compound Ia is called compound Ia. 2 The compound Ib is a compound in which a hydrogen atom is bonded to the bond to the group P. 1 and group A 2 When a compound in which a hydrogen atom is bonded to each bond of the compound Ia is defined as compound II, the absolute value of the difference between the HOMO energy of the compound Ia and the HOMO energy of the compound II and the absolute value of the difference between the HOMO energy of the compound Ib and the HOMO energy of the compound II are both 2.75 eV or more and 3.90 eV or less.

[0101] [ka]

[0102] In formula (n2), Ar 4 ~Ar 6 each independently represents a divalent aromatic carbocyclic group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent.

[0103] The composition of the present disclosure can suppress dark current in a photoelectric conversion element and absorb light of long wavelengths. The action of the composition of the present disclosure is not clear, but is presumed to be as follows.

[0104] The LUMO energy of the p-type semiconductor material contained in the composition of the present disclosure is −3.35 eV or more and −2.75 eV or less. When the LUMO energy of the p-type semiconductor material is within the above range, when it is combined with the n-type semiconductor material, the photoelectric conversion element absorbs long-wavelength light and performs photoelectric conversion while suppressing dark current. The principle by which dark current is suppressed by such a combination is unclear, but it is thought that by combining the HOMO energy range of the n-type semiconductor material and the LUMO energy range of the p-type semiconductor material within specific ranges, the charge mobility is improved, allowing long-wavelength light to be absorbed and photoelectric conversion to be performed, and the dark current is suppressed, partly due to the suppression of charge injection from the electrode.

[0105] Furthermore, the n-type semiconductor material contained in the composition of the present disclosure is a compound represented by the above formula (n1), Base A 1 The compound in which a hydrogen atom is bonded to the bond to the group P of the compound Ia is called compound Ia. 2 The compound Ib is a compound in which a hydrogen atom is bonded to the bond to the group P. 1 and group A 2 When a compound in which a hydrogen atom is bonded to each bond of the compound Ia is defined as compound II, the absolute value of the difference between the HOMO energy of the compound Ia and the HOMO energy of the compound II and the absolute value of the difference between the HOMO energy of the compound Ib and the HOMO energy of the compound II are both 2.75 eV or more and 3.90 eV or less. That is, in n-type semiconductor materials, A, which is an electron-withdrawing and an acceptor, 1 The absolute value of the difference in HOMO energy between P and P, and the electron-withdrawing and electron-accepting A 2 The absolute value of the difference in HOMO energy between and P (ΔE H-H) is within the above range, the π electrons in the n-type semiconductor material are likely to be delocalized, so the n-type semiconductor material of the present disclosure can absorb light of long wavelengths (for example, in the short-wave infrared region).

[0106] Therefore, the composition of the present disclosure combining the p-type semiconductor material and the n-type semiconductor material defined as above suppresses the dark current in the photoelectric conversion element and can absorb light of long wavelengths. Note that the present disclosure is not limited to the above estimation mechanism at all.

[0107] <p-type semiconductor material> In the composition of the present disclosure, the p-type semiconductor material includes a structural unit X represented by the following formula and a structural unit Y which is a divalent group and has a chemical structure different from that of the structural unit X. The LUMO energy of the p-type semiconductor material is -3.35 eV or more and -2.75 eV or less. <U+

[0108] <U+ <U+

Chemical formula

[0109] In the structural unit X, <U+ Ar 1 and Ar 3 each independently represents a trivalent aromatic carbocyclic group which may have a substituent or a trivalent aromatic heterocyclic group which may have a substituent. <U+ Ar 2 each independently represents a tetravalent aromatic carbocyclic group which may have a substituent or a tetravalent aromatic heterocyclic group which may have a substituent. <U+ n is an integer of any one of 0 to 3. <U+ <U+

[0110] <U+ [LUMO energy]<U+ The LUMO energy of the p-type semiconductor material is -3.35 eV or more and -2.75 eV or less. From the viewpoint of suppressing dark current, the LUMO energy is preferably -3.34 eV or more, more preferably -3.33 eV or more, even more preferably -3.32 eV or more, and particularly preferably -3.31 eV or more. From the viewpoint of suppressing dark current, the LUMO energy is preferably -2.85 eV or less, more preferably -2.90 eV or less, even more preferably -2.95 eV or less, and particularly preferably -3.00 eV or less.

[0111] In the present disclosure, the LUMO energy of a p-type semiconductor material is calculated based on a value measured by ultraviolet photoelectron spectroscopy (UPS method). The calculation method will be specifically described below.

[0112] (1) Sample preparation First, a p-type semiconductor material was dissolved in orthodichlorobenzene at 0.5% by mass or 1.0% by mass to obtain a solution, which was then applied to a glass substrate by spin coating to form a coating film, which was then dried on a hot plate at 70°C to form a layer with a thickness of 100 nm, which was used as a sample.

[0113] (2) Measurement of HOMO energy and calculation of LUMO energy by UPS method The HOMO energy of the p-type semiconductor material is calculated based on the number of electrons measured for the obtained sample by the UPS method using a photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd., Model AC-2) in air.

[0114] The UPS method is a method for measuring the number of photoelectrons emitted in response to the energy of ultraviolet light irradiated onto a solid surface. From the minimum energy at which photoelectrons are generated, the work function can be estimated if the sample is a metal, or the HOMO energy if the sample is a semiconductor material.

[0115] The LUMO energy of a p-type semiconductor material can be calculated using the following formula. Formula: LUMO energy = band gap (Eg) - HOMO energy

[0116] Here, the band gap (Eg) can be calculated using the following formula based on the absorption edge wavelength of the p-type semiconductor material. Formula: Band gap (Eg) = hc / absorption edge wavelength In the formula, h represents Planck's constant (h = 6.626 × 10 -34 Js), c represents the speed of light (c=3×10 8 m / s).

[0117] The absorption edge wavelength is measured using a spectrophotometer capable of measuring in the wavelength regions of ultraviolet, visible, and near-infrared light (for example, an ultraviolet-visible-near-infrared spectrophotometer Cary5E manufactured by Agilent).

[0118] In an absorption spectrum obtained by a spectrophotometer, that is, an absorption spectrum plotted with the absorbance (absorption intensity) of a compound on the vertical axis and the wavelength on the horizontal axis, the absorption edge wavelength (nm) is defined as the wavelength value at the intersection of the baseline and a straight line fitted to the shoulder (high wavelength side) of the absorption peak.

[0119] [Chemical structure] (Constituent unit X) The p-type semiconductor material contains a structural unit X represented by the following formula:

[0120] [ka]

[0121] In the structural unit X, Ar 1 and Ar 3 each independently represents an optionally substituted trivalent aromatic carbocyclic group or an optionally substituted trivalent aromatic heterocyclic group. From the viewpoint of suppressing dark current, Ar 1 and Ar 3are each independently a trivalent aromatic heterocyclic group which may have a substituent. The aromatic heterocyclic group is preferably an aromatic heterocyclic group containing at least one of a sulfur atom and a nitrogen atom as a heteroatom, more preferably an aromatic heterocyclic group containing a sulfur atom and a nitrogen atom, and even more preferably a 5-membered aromatic heterocyclic group containing a sulfur atom and a nitrogen atom. stomach.

[0122] In the structural unit X, Ar 2 each independently represents an optionally substituted tetravalent aromatic carbocyclic group or an optionally substituted tetravalent aromatic heterocyclic group. From the viewpoint of suppressing dark current, Ar 2 is preferably a tetravalent aromatic carbocyclic group which may have a substituent, more preferably a tetravalent 6-membered aromatic carbocyclic group.

[0123] From the viewpoint of suppressing dark current, in the structural unit X, Ar 1 ~Ar 3 At least one of Ar is preferably an aromatic heterocyclic group containing at least one of a sulfur atom and a nitrogen atom. 1 ~Ar 3 It is more preferable that two of them are aromatic heterocyclic groups containing at least one of a sulfur atom and a nitrogen atom, further preferably aromatic heterocyclic groups containing a sulfur atom and a nitrogen atom, and particularly preferably aromatic heterocyclic groups containing a sulfur atom and a nitrogen atom.

[0124] Ar 1 ~Ar 3 is preferably a monocyclic ring. In the structural unit X, Ar 2 When there are a plurality of, they may be the same or different.

[0125] In the structural unit X, n is an integer of 0 to 3. From the viewpoint of suppressing dark current, n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0126] The structural unit X preferably has a structure represented by the following formula (X1).

[0127] [ka]

[0128] In formula (X1), n ​​is an integer of 0 to 3. From the viewpoint of suppressing dark current, n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0129] The p-type semiconductor material may contain only one type of structural unit X, or may contain two or more different types. The p-type semiconductor material may contain only one type of structural unit represented by formula (X1), or may contain two or more different types.

[0130] (structural unit Y) The p-type semiconductor material contains a structural unit Y which is a divalent group and has a different chemical structure from the structural unit X. The structural unit Y is preferably a divalent aromatic carbocyclic group which may have a substituent, or a divalent aromatic heterocyclic group which may have a substituent. The aromatic carbocyclic group may be either a monocyclic aromatic carbocyclic group or a condensed ring aromatic carbocyclic group. From the viewpoint of suppressing dark current, the aromatic heterocyclic group is preferably an aromatic heterocyclic group containing at least one of a sulfur atom and a nitrogen atom, and more preferably an aromatic heterocyclic group containing a sulfur atom. The aromatic heterocyclic group may be either a monocyclic aromatic heterocyclic group or a fused ring aromatic heterocyclic group.

[0131] The structural unit Y is also preferably a structural unit represented by any one of formulas (I) to (VI) described below.

[0132] The p-type semiconductor material may contain only one type of structural unit Y, or may contain two or more different types.

[0133] (Formula (I) ~ Formula (III)) The p-type semiconductor material of the present disclosure is also preferably a polymer compound containing at least one selected from the group consisting of a constitutional unit represented by the following formula (I), a constitutional unit represented by the following formula (II), and a constitutional unit represented by the following formula (III):

[0134] [ka]

[0135] -Formula (I)- In formula (I), Ar 9 and Ar 10 represents an optionally substituted trivalent aromatic heterocyclic group.

[0136] Ar 9 and Ar 10 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.

[0137] Ar 9 and Ar 10 The aromatic heterocycles that can constitute Ar may each be a single ring or a condensed ring. 9 and Ar 10 are preferably monocyclic. 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.

[0138] 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. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 9 and Ar 10 The aromatic heterocyclic ring that can constitute the above is preferably a thiophene ring or a thiazole ring.

[0139] In formula (I), Z represents a group represented by the following formulae (Z-1) to (Z-7).

[0140] [ka]

[0141] In formulas (Z-1) to (Z-7), R 1 each independently represents any group of the "side chain A" of the present disclosure, and R 1 If there are two, then two R 1 may be the same or different.

[0142] From the viewpoint of suppressing dark current, R 1 are each more preferably independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted monovalent heterocyclic group.

[0143] The constitutional unit represented by formula (I) is preferably a constitutional unit represented by the following formulas (I-1) to (I-5).

[0144] [ka]

[0145] In formulas (I-1) to (I-5), Ar 9 and Ar 10 The definition of Ar in formula (I) 9 and Ar 10 In formulas (I-1) to (I-5), R 1 The definition and preferred embodiments of R in formula (I) 1 The definition and preferred embodiments are the same as those of R. 1 If there are two, there are two R 1 may be the same or different.

[0146] From the viewpoint of suppressing dark current, formula (I) is preferably formula (I-4).

[0147] The p-type semiconductor material may contain only one type of constitutional unit represented by formula (I), or may contain two or more different types, or may contain two or more of the same type.

[0148] Specific examples of the constitutional unit represented by formula (I) include groups represented by formulas 1 to 152 described in paragraphs

[0098] to

[0115] of JP-A No. 2012-107187.

[0149] The constitutional unit represented by formula (I) is preferably a constitutional unit represented by any one of the following formulae (I-1-1) to (I-1-7), (I-2-1) to (I-2-4), (I-3-1) to (I-3-2), and (I-4-1) to (I-4-2).

[0150] [ka]

[0151] In the above formulas (I-1-1) to (I-1-7), formulas (I-2-1) to (I-2-4), formulas (I-3-1) to (I-3-2), and formulas (I-4-1) to (I-4-2), R 1 The definition and preferred embodiments of R in formula (I) 1 The definition and preferred embodiments are the same as those of R. 1 If there are multiple R 1may be the same or different from each other. From the viewpoint of suppressing dark current, it is more preferable that formula (I) is any one of formula (I-1-1), formulas (I-1-4) to (I-1-7), formula (I-2-1), formula (I-2-4), formulas (I-3-1) to (I-3-2), and formulas (I-4-1) to (I-4-2).

[0152] More specific examples of preferred structural units represented by formula (I) include structural units represented by the following formulas.

[0153] [ka]

[0154] -Formula (II)- In formula (II), Ar 11 represents an optionally substituted divalent monocyclic aromatic carbocyclic group or an optionally substituted divalent monocyclic aromatic heterocyclic group.

[0155] A specific example of a monocyclic aromatic carbon ring is a benzene ring. From the viewpoint of suppressing dark current, Ar 11 The monocyclic aromatic carbocyclic ring that can constitute the above is preferably a benzene ring.

[0156] Specific examples of the monocyclic aromatic heterocycle include a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 11 The monocyclic aromatic heterocycle that can constitute the above is preferably a thiophene ring or a thiazole ring.

[0157] The constitutional unit represented by formula (II) is preferably a constitutional unit represented by any one of the following formulae (II-1) to (II-8).

[0158] [ka]

[0159] In formulas (II-1) to (II-8), R 2 R each independently represents any group of the "side chain A" of the present disclosure. 2 If there are multiple R 2 may be the same or different from each other.

[0160] From the viewpoint of suppressing dark current, formula (II) is preferably formula (II-1) or (II-8). 2 are each independently preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, or an alkylthio group having 1 to 30 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent. 2 It is more preferable that one of the groups is a hydrogen atom and the other is an alkyl group which may have a substituent.

[0161] The p-type semiconductor material may contain only one type of constitutional unit represented by formula (II), or may contain two or more different types, or may contain two or more of the same type.

[0162] -Formula (III)- In formula (III), in formula (III), Ar 12 and Ar 13 each independently represents an aromatic carbocyclic group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and m represents an integer of 1 or more.

[0163] When m is 1, Ar 12 and Ar 13 each independently represents an optionally substituted trivalent aromatic carbocyclic group or an optionally substituted trivalent aromatic heterocyclic group. When m is 2 or more, Ar 12represents an optionally substituted trivalent aromatic carbocyclic group or an optionally substituted trivalent aromatic heterocyclic group. When m is 2 or more, the terminal Ar 13 represents an optionally substituted trivalent aromatic carbocyclic group or an optionally substituted trivalent aromatic heterocyclic group, and Ar 12 and terminal Ar 13 Ar exists between 13 represents an optionally substituted tetravalent aromatic carbocyclic group or an optionally substituted tetravalent aromatic heterocyclic group.

[0164] Specific examples of aromatic carbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 12 and Ar 13 The aromatic carbon ring that can constitute the above is preferably a benzene ring or a naphthalene ring.

[0165] 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. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 12 and Ar 13 The aromatic heterocyclic ring that can constitute the above is preferably a thiophene ring, a furan ring or a thiazole ring.

[0166] Ar 12 and Ar 13 is preferably a monocyclic ring. In formula (III), Ar 13 When there are a plurality of, they may be the same or different.

[0167] From the viewpoint of suppressing dark current, m is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0168] The p-type semiconductor material may contain only one type of constitutional unit represented by formula (III), or may contain two or more different types, or may contain two or more of the same type.

[0169] Specific examples of the constitutional unit represented by formula (III) include groups represented by formulas 201 to 234 described in paragraphs

[0116] to

[0121] of JP-A No. 2012-107187.

[0170] The constitutional unit represented by formula (III) is preferably a constitutional unit represented by any one of the following formulae (III-1) to (III-14).

[0171] [ka]

[0172] In formulas (III-1) to (III-14), R 3 R each independently represents any group of the "side chain A" of the present disclosure. 3 If there are multiple R 3 may be the same or different from each other.

[0173] From the viewpoint of suppressing dark current, formula (III) is preferably formula (III-6), formula (III-9), or formula (III-11). 3 are each independently preferably a hydrogen atom or an optionally substituted thiophene ring group, more preferably a hydrogen atom or a thiophene ring group optionally substituted with an alkyl group having 1 to 20 carbon atoms.

[0174] -Formula (IV)- The p-type semiconductor material of the present disclosure may include a constitutional unit represented by the following formula (IV):

[0175] [ka]

[0176] In formula (IV), Ar 14 represents an optionally substituted tetravalent aromatic carbocyclic group or an optionally substituted tetravalent aromatic heterocyclic group, Ar 15 represents an aromatic carbocyclic group which may have a substituent or an aromatic heterocyclic group which may have a substituent; and q represents an integer of 1 to 5.

[0177] When q is 1, Ar 15 represents an optionally substituted divalent aromatic carbocyclic group or an optionally substituted divalent aromatic heterocyclic group. When q is an integer between 2 and 5, the terminal Ar 15 represents a divalent aromatic carbocyclic group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent, and Ar 14 and terminal Ar 15 Ar exists between 15 represents an optionally substituted tetravalent aromatic carbocyclic group or an optionally substituted tetravalent aromatic heterocyclic group.

[0178] Specific examples of aromatic carbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 14 The aromatic carbon ring that can constitute the Ar group is preferably a benzene ring or a naphthalene ring. 15 The aromatic carbon ring that can constitute the above is preferably a benzene ring or a naphthalene ring.

[0179] 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. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 14 The aromatic heterocycle that can constitute the compound is preferably a thiophene ring, a pyridine ring, or a furan ring. 15 The aromatic heterocyclic ring that can constitute the above is preferably an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, or a pyrazine ring.

[0180] Ar 14 and Ar 15 is preferably a monocyclic ring. In formula (IV), Ar 15 When there are a plurality of, they may be the same or different.

[0181] From the viewpoint of suppressing dark current, q is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0182] The p-type semiconductor material may contain only one type of constitutional unit represented by formula (IV), or may contain two or more different types, or may contain two or more of the same type.

[0183] Specific examples of the constitutional unit represented by formula (IV) include groups represented by formulas 301 to 323 described in paragraphs

[0124] to

[0127] of JP-A No. 2012-107187.

[0184] The constitutional unit represented by formula (IV) is preferably a constitutional unit represented by any one of the following formulae (IV-1) to (IV-13).

[0185] [ka]

[0186] In formulas (IV-1) to (IV-13), R 4 R each independently represents any group of the "side chain A" of the present disclosure. 4 If there are multiple R 4 may be the same or different from each other.

[0187] From the viewpoint of suppressing dark current, formula (IV) is preferably formula (IV-7), (IV-8), or (IV-12). In formulas (IV-7), (IV-8), and (IV-12), R 4 are each independently preferably a hydrogen atom, a halogen atom or an alkyl group which may have a substituent, more preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.

[0188] When the composition of the present disclosure is used in a photoelectric conversion element, from the viewpoint of increasing photoelectric conversion efficiency, the p-type semiconductor material of the present disclosure preferably contains at least one of the structural units represented by formula (I) and the structural unit represented by formula (IV) among the structural units represented by formulas (I) to (IV), and more preferably contains the structural unit represented by formula (I).

[0189] -Formula (V)- The p-type semiconductor material of the present disclosure may contain a structural unit other than the structural units represented by formulas (I) to (IV), and may contain, for example, a structural unit represented by any of the following formulas (V-1) to (V-2).

[0190] [ka]

[0191] In formula (V-2), R 5 R each independently represents any group of the "side chain A" of the present disclosure. 5 If there are multiple R 5 may be the same or different.

[0192] From the viewpoint of suppressing dark current, in formula (V-2), R 5 are each independently preferably a hydrogen atom or an alkyl group or alkoxy group which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.

[0193] -Formula (VI)- The p-type semiconductor material of the present disclosure may have a group in which two or more types of structural units represented by formulas (I) to (V) are bonded together. Examples of such groups include groups represented by formulas 401 to 414 described in paragraphs

[0131] to

[0134] of JP 2012-107187 A.

[0194] The group in which two or more types of constitutional units represented by formulae (I) to (V) are bonded is preferably a group represented by the following formula (VI-1).

[0195] [ka]

[0196] In formula (VI-1), R 6 each independently represents any group of the "side chain A" of the present disclosure, and a and b each independently represent an integer of 1 to 5. R 6 If there are multiple R 6 may be the same or different. a and b may be the same or different.

[0197] From the viewpoint of suppressing dark current, in formula (VI-1), R 6 are each independently preferably a hydrogen atom, a halogen atom which may have a substituent, an alkyl group, an alkoxy group, or an alkylthio group, and more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. a and b are each independently preferably an integer of 1 to 3, and more preferably 1.

[0198] -Mole % of structural units- In the p-type semiconductor material of the present disclosure, the total content of the structural units represented by formulas (I) to (IV) is preferably 1 mol % to 100 mol %, more preferably 10 mol % to 100 mol %, even more preferably 30 mol % to 100 mol %, particularly preferably 50 mol % to 100 mol %, even more preferably 70 mol % to 100 mol %, and most preferably 90 mol % to 100 mol %, relative to the total content of the structural units contained in the p-type semiconductor material.

[0199] In the p-type semiconductor material of the present disclosure, the content of the structural unit represented by formula (I) is preferably 1 mol % to 90 mol %, more preferably 10 mol % to 80 mol %, and even more preferably 30 mol % to 70 mol %, relative to the total content of structural units contained in the p-type semiconductor material.

[0200] In the p-type semiconductor material of the present disclosure, the content of the structural unit represented by formula (II) is preferably 1 mol % to 90 mol %, more preferably 10 mol % to 80 mol %, and even more preferably 30 mol % to 70 mol %, relative to the total content of structural units contained in the p-type semiconductor material.

[0201] In the p-type semiconductor material of the present disclosure, the content of the structural unit represented by formula (III) is preferably 1 mol % to 90 mol %, more preferably 10 mol % to 80 mol %, and even more preferably 30 mol % to 70 mol %, relative to the total content of structural units contained in the p-type semiconductor material.

[0202] In the p-type semiconductor material of the present disclosure, the content of the structural unit represented by formula (IV) is preferably 1 mol % to 90 mol %, more preferably 10 mol % to 80 mol %, and even more preferably 30 mol % to 70 mol %, relative to the total content of structural units contained in the p-type semiconductor material.

[0203] The p-type semiconductor material of the present disclosure may contain other structural units in addition to the structural units represented by formulas (I) to (IV). When the p-type semiconductor material of the present disclosure contains other structural units, the content of the other structural units is preferably 0 mol % to 30 mol %, more preferably 0 mol % to 20 mol %, even more preferably 0 mol % to 10 mol %, and particularly preferably 0 mol %, relative to the total content of structural units contained in the p-type semiconductor material.

[0204] <Specific Examples of p-Type Semiconductor Materials of the Present Disclosure> From the viewpoint of suppressing dark current, the p-type semiconductor material of the present disclosure is preferably a polymer compound containing at least two types selected from the group consisting of a structural unit represented by formula (I), a structural unit represented by formula (II), and a structural unit represented by formula (III), and more preferably a polymer compound containing two types selected from the group consisting of a structural unit represented by formula (I), a structural unit represented by formula (II), and a structural unit represented by formula (III).

[0205] In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. The p-type semiconductor material of the present disclosure preferably comprises a structural unit represented by formula (I-4), a structural unit represented by formula (II-1), and at least one structural unit selected from the group consisting of formulas (III-6), (III-9), and (III-11).

[0206] Specific examples of the p-type semiconductor material of the present disclosure are described below, but the p-type semiconductor material of the present disclosure is not limited thereto.

[0207] [ka]

[0208] [ka]

[0209]

change

[0210]

change

[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0217]

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[0218] [Weight average molecular weight] The weight-average molecular weight of the p-type semiconductor material of the present disclosure is preferably 6,000 to 300,000, more preferably 7,000 to 150,000, and even more preferably 8,000 to 80,000. In the present disclosure, the weight-average molecular weight is a polystyrene-equivalent weight-average molecular weight determined by size exclusion chromatography (SEC).

[0219] [Method of manufacturing p-type semiconductor material] The method for producing the p-type semiconductor material of the present disclosure preferably involves reacting a compound represented by the following formula (IR) with a compound represented by the following formula (Y1-R).

[0220] [ka]

[0221] In formula (IR), Z 1 is a divalent group, and Ar R1 and Ar R2 each independently represents a trivalent aromatic hydrocarbon ring group or a trivalent heterocyclic group. In formula (IR), X R represents a boron-containing group. Examples of the boron-containing group include an atomic group represented by the following formula (XR-1): In formula (XR-1), * represents a bond.

[0222] [ka]

[0223] In formula (Y1-R), Ar Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are bonded together, and these groups may have a substituent. In formula (Y1-R), Y R each independently represents a halogen atom.

[0224] In the method for producing the p-type semiconductor material of the present disclosure, the method of reacting the compound represented by the formula (I-R) with the compound represented by the formula (Y1-R) is not particularly limited, but from the viewpoint of ease of synthesis of the p-type semiconductor material, a method using a Suzuki-Miyaura coupling reaction or a Stille coupling reaction is preferable. Examples of the method for performing the Suzuki-Miyaura coupling reaction or the Stille coupling reaction include a method of reacting in an arbitrary solvent using a palladium catalyst as a catalyst in the presence of a base.

[0225] [Other p-type semiconductor materials] The composition of the present disclosure may contain a p-type semiconductor material other than the p-type semiconductor material of the present disclosure described above. The type of the p-type semiconductor material other than the p-type semiconductor material of the present disclosure is not particularly limited.

[0226] <n-type semiconductor material> In the composition of the present disclosure, the n-type semiconductor material is a compound represented by the following formula (n1), A 1 -P-A 2 (n1) (In the formula (n1), A 1 and A 2 are each independently an electron-withdrawing monovalent group, and P is a divalent group having a structure represented by the following formula (n2).) The compound in which a hydrogen atom is bonded to the bond of the group A 1 to the group P is defined as compound Ia, and the compound in which a hydrogen atom is bonded to the bond of the group A 2 to the group P is defined as compound Ib. When the compound in which hydrogen atoms are bonded to the bonds of the group P to the group A 1 and the group A 2 is defined as compound II, the absolute value of the difference between the HOMO energy of the compound Ia and the HOMO energy of the compound II, and the absolute value of the difference between the HOMO energy of the compound Ib and the HOMO energy of the compound II are both 2.75 eV or more and 3.90 eV or less.

[0227] [Chemical formula]

[0228] In formula (n2), Ar 4 ~Ar 6 each independently represents a divalent aromatic carbocyclic group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent.

[0229] [HOMO energy] (ΔE H-H ) The n-type semiconductor material of the present disclosure is a compound represented by the formula (n1): 1 The compound in which a hydrogen atom is bonded to the bond to the group P of the compound Ia is called compound Ia. 2 The compound Ib is a compound in which a hydrogen atom is bonded to the bond to the group P. 1 and group A 2 When a compound with hydrogen atoms bonded to each bond of Ia and II is called compound II, the absolute value of the difference between the HOMO energy of compound Ia and that of compound II (ΔE H-H ), and the absolute value of the difference between the HOMO energy of compound Ib and the HOMO energy of compound II (ΔE H-H ) is between 2.75 eV and 3.90 eV.

[0230] Specifically, compound Ia is A 1 Compound Ib is a compound represented by A 2 Compound II is a compound represented by —H, and compound II is a compound represented by HPH.

[0231] The n-type semiconductor material of the present disclosure has the above ΔE H-H are both 2.75 eV or more, and therefore, when the compound of the present disclosure is used in a photoelectric conversion element, photoelectric conversion can be performed with light of a long wavelength, for example, a wavelength of 1300 nm.

[0232] The above ΔE H-His preferably 2.80 eV or more and 3.88 eV or less, more preferably 3.00 eV or more and 3.85 eV or less, even more preferably 3.30 eV or more and 3.85 eV or less, and particularly preferably 3.50 eV or more and 3.83 eV or less.

[0233] The HOMO energy of the n-type semiconductor material of the present disclosure can be calculated by any suitable conventional computational science method. For example, a computational science method can be used in which the quantum chemistry calculation program Gaussian 03 is used, ground state structure is optimized by density functional theory at the B3LYP level, and 6-31g* is used as the basis function. In the present disclosure, unless otherwise specified, values ​​calculated by this quantum chemistry calculation are used.

[0234] [HOMO-LUMO gap] The n-type semiconductor material of the present disclosure preferably has a HOMO-LUMO gap of less than 1.6 eV, more preferably 1.5 eV or less. The HOMO-LUMO gap refers to the absolute value of the difference between the HOMO energy and the LUMO energy. The HOMO-LUMO gap may be calculated by measurement, but in the present disclosure, a value calculated by quantum chemical calculation is used.

[0235] When the HOMO-LUMO gap is less than 1.6 eV (more preferably 1.5 eV or less), the compound of the present disclosure can perform photoelectric conversion at longer wavelengths when used in a photoelectric conversion element.

[0236] The HOMO-LUMO gap is more preferably 1.45 eV or less, and even more preferably 1.42 eV or less. The lower limit of the HOMO-LUMO gap is not particularly limited, but is, for example, 1 eV.

[0237] [Energy difference between the energy level of the lowest excited singlet state of a compound and the energy level of the ground state (E_S1)] The n-type semiconductor material of the present disclosure preferably has an energy difference (E_S1) between the energy level of the lowest excited singlet state and the energy level of the ground state calculated by a computational science method of 1.5 eV or less. The computational science method may be, for example, a method of calculation using a quantum chemistry calculation program. In the examples described below, the following method is used.

[0238] Using the quantum chemistry calculation program Gaussian 03, the ground state structure is optimized using the density functional method at the B3LYP level, and the value obtained by calculating the optimized structure using 6-31g* as the basis function is taken as the value of the ground state energy level. Next, the energy level of the lowest exciton singlet state is determined by TD DFT calculation using B3LYP as the functional and 6-31g* as the basis function. The difference between the energy level of the lowest exciton singlet state and the energy level of the ground state is taken as the energy band gap (E_S1).

[0239] When the energy band gap (E_S1) of the n-type semiconductor material is 1.5 eV or less, the compound of the present disclosure can perform photoelectric conversion at longer wavelengths when used in a photoelectric conversion element.

[0240] The energy band gap (E_S1) of the n-type semiconductor material is more preferably 1.47 eV or less, even more preferably 1.45 eV or less, and even more preferably 1.42 eV or less. The lower limit of the energy band gap (E_S1) of the n-type semiconductor material is not particularly limited, but is, for example, 1 eV.

[0241] [Chemical structure] (Formula (n1)) -A 1 , A 2 - In the n-type semiconductor material of the present disclosure, A in formula (n1) 1 and A 2 are each independently an electron-withdrawing monovalent group. 1 and A 2may be the same group or different groups. From the viewpoint of facilitating the synthesis of the compounds of the present disclosure, A 1 and A 2 are preferably the same group.

[0242] A 1 and A 2 Examples of the group include a group represented by -CH=C(-CN)2 and a group represented by any one of the following formulae (a-1) to (a-9).

[0243] [ka]

[0244] In formulas (a-1) to (a-7), T 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.

[0245] Examples of the carbocyclic ring represented by T which may have a substituent include aromatic carbocyclic rings, preferably aromatic carbocyclic rings. Specific examples of the carbocyclic ring represented by T which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, preferably a benzene ring, a naphthalene ring, and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0246] Examples of the heterocycle represented by T which may have a substituent include aromatic heterocycles, preferably aromatic carbocycles. Specific examples of the heterocycle represented by T which may have a substituent include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a thienothiophene ring, a quinoline ring, a quinoxaline ring, a pyridopyrazine ring, and a pyrazinopyrazine ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, a thienothiophene ring, a quinoxaline ring, a pyridopyrazine ring, and a pyrazinopyrazine ring, more preferably a pyridine ring, a pyrazine ring, a quinoxaline ring, a pyridopyrazine ring, and a pyrazinopyrazine ring. These rings may have a substituent.

[0247] Examples of the substituent that the carbocyclic ring or heterocyclic ring represented by T 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.

[0248] X 4 , X 5 , and X 6 each independently represents an oxygen atom, a sulfur atom, an alkylidene group, or a group represented by ═C(—CN) 2 , and is preferably an oxygen atom, a sulfur atom, or a group represented by ═C(—CN) 2 .

[0249] X 7 represents a hydrogen atom or a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or a monovalent heterocyclic group. 7 is preferably a cyano group.

[0250] R a1 , R a2 , R a3 , R a4, and R a5 each independently represents a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyloxy group, an optionally substituted aryl group, or a monovalent heterocyclic group, and is preferably an optionally substituted alkyl group or an optionally substituted aryl group.

[0251] [ka]

[0252] In formula (a-8) and formula (a-9), R a6 and R a7 each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted monovalent aromatic carbocyclic group, or an optionally substituted monovalent aromatic heterocyclic group, a6 and R a7 may be the same or different from each other.

[0253] Among them, A 1 and A 2 The electron-withdrawing monovalent group represented by the formula (a-1) is preferably a group represented by the formula (a-1).

[0254] A 1 and A 2 Specific examples of the electron-withdrawing monovalent group represented by the formula (a-1-1) include groups represented by the following formulas (a-1-9), (a-5-1), (a-6-1), (a-6-2) and (a-7-1).

[0255] [ka]

[0256] In formulas (a-1-1) to (a-1-9), (a-5-1), (a-6-1), (a-6-2) and (a-7-1), Multiple R's a10 each independently represents a hydrogen atom or a substituent, R a1 , R a2 , R a3 , R a4 , and R a5 are each independently as defined above.

[0257] R a10 is preferably a hydrogen atom, a halogen atom, an alkyloxy group, a cyano group or an alkyl group, and more preferably a fluorine atom or a cyano group. a1 , R a2 , R a3 , R a4 , and R a5 is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.

[0258] Among them, A 1 and A 2 The electron-withdrawing monovalent group represented by the formula (a-1-1) is preferably a group represented by any one of the formulas (a-1-5) to (a-1-9).

[0259] A 1 and A 2 are preferably each independently an electron-withdrawing group containing one or more groups selected from the group consisting of a halogen atom, a cyano group, a carbonyl group, and a thiocarbonyl group.

[0260] A 1 and A 2 Preferred examples of the electron-withdrawing monovalent group represented by the formula include groups represented by the following formulas.

[0261] [ka]

[0262] [ka]

[0263] (Formula (n2)) -Ar 4 , Ar 6 - Ar in formula (n2) 4 and Ar 6 are each independently a divalent aromatic carbocyclic group which may have a substituent and which may have a plurality of further condensed ring structures, or a divalent aromatic heterocyclic group which may have a substituent and which may have a plurality of further condensed ring structures, and the divalent aromatic carbocyclic group and the divalent aromatic heterocyclic group have three or less double bonds in the main chain, i.e., the conjugated structure connecting two bonds over the shortest distance.

[0264] From the viewpoint of solubility, the divalent aromatic carbocyclic group and the divalent aromatic heterocyclic group preferably have two double bonds in the conjugated structure that connects two bonds in the shortest distance.

[0265] Ar 4 and Ar 6 is preferably a divalent aromatic heterocyclic group that contains a thiophene ring and may have a substituent and may have a plurality of condensed ring structures.

[0266] Ar 4 and Ar 6 The number of carbon atoms in the divalent aromatic carbocyclic group represented by the following formula (I) is usually 6 to 60, not including the number of carbon atoms in the substituent, and preferably 6 to 20. The number of carbon atoms in the aromatic carbocyclic group including the substituent is usually 6 to 100.

[0267] Ar 4 and Ar 6 Examples of the divalent aromatic carbocyclic group represented by the formula include the divalent aromatic carbocyclic group represented by the formula below: The divalent aromatic carbocyclic group represented by the formula below may further have a substituent.

[0268] [ka]

[0269] Ar 4 and Ar 6 The divalent aromatic heterocyclic group represented by the following formula (I) typically has 2 to 60 carbon atoms, preferably 4 to 60 carbon atoms, and more preferably 4 to 20 carbon atoms.

[0270] Ar 4 and Ar 6 Examples 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.

[0271] Ar 4 and Ar 6 Specific examples of the divalent aromatic heterocyclic group represented by the formula include divalent aromatic heterocyclic groups represented by the formula below: These groups may further have a substituent.

[0272] [ka]

[0273] [ka]

[0274] [ka]

[0275] Ar 4 and Ar 6 The divalent aromatic heterocyclic group represented by the formula below is preferably a divalent aromatic heterocyclic group represented by the formula below: These groups may further have a substituent.

[0276] [ka]

[0277] Ar represented by the above formula 4 and Ar 6 Preferred specific examples of the divalent aromatic heterocyclic group represented by the formula include divalent groups represented by the formula below.

[0278] [ka]

[0279] (Formula (n3)) Ar in formula (n2) 5 is preferably a structure represented by the following formula (n3).

[0280] [ka]

[0281] In formula (n3), X 2 represents a divalent group, Ar 7 and Ar 8 each independently represent an optionally substituted fused or non-fused trivalent aromatic carbocyclic group, or an optionally substituted fused or non-fused trivalent aromatic heterocyclic group, c and d each independently represent 0 or 1.

[0282] -X 2 - In formula (n3), X 2 is a divalent group. 2is preferably a group represented by -S-, a group represented by -CR1R2-, a group represented by -SiR1R2-, a group represented by -NR3-, a group represented by -C(=O)-, a group represented by -C(=O)-NR3-, a group represented by -NR3-C(=O)-, a group represented by -CR1R2-O-, a group represented by -O-CR1R2-, a group represented by -C(=O)-CR1R2- or a group represented by -CR1R2-C(=O)-.

[0283] R1, R2, and R3 each independently represent any group of the "Side Chain A" of the present disclosure.

[0284] Among them, X 2 is preferably a group represented by -CR1R2-, a group represented by -O-CR1R2-, or a group represented by -CR1R2-O-, and more preferably a group represented by -O-CR1R2- or a group represented by -CR1R2-O-.

[0285] From the viewpoint of solubility, it is preferable that R1 and R2 do not combine with each other to form a ring.

[0286] From the viewpoint of solubility, R1 and R2 are preferably alkyl groups which may have a substituent. The alkyl groups preferably have 3 to 50 carbon atoms, more preferably 4 to 40 carbon atoms.

[0287] R1 and R2 may be the same or different from each other, but from the viewpoint of ease of synthesis, it is preferable that R1 and R2 are the same.

[0288] -Ar 7 , Ar 8 - In formula (n3), Ar 7 and Ar 8 each independently represents an optionally substituted fused or non-fused trivalent aromatic carbocyclic group, or an optionally substituted fused or non-fused trivalent aromatic heterocyclic group.

[0289] Specific examples of aromatic carbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 7 and Ar 8 The aromatic carbon ring that can constitute the above is preferably a benzene ring or a naphthalene ring.

[0290] Specific examples of the aromatic heterocycle include a thiophene ring, a thiazole ring, a furan ring, an oxazole ring, a cyclopentathiophene ring, a cyclopentadithiophene ring, a benzothiophene ring, a pyrrole ring, a benzopyrrole ring, a thienopyrrole ring, a thienosilole ring, a benzosilole ring, a thiazole ring, and a quinoxaline ring. These rings may have a substituent. From the viewpoint of suppressing dark current, Ar 7 and Ar 8 The aromatic heterocycle that can constitute the above is preferably a thiophene ring or a cyclopentadithiophene ring.

[0291] -c, d- In formula (n3), c and d each independently represent 0 or 1. From the viewpoint of suppressing dark current, it is preferable that c and d are 0, or c is 0 and d is 1.

[0292] <Specific Examples of n-Type Semiconductor Materials of the Present Disclosure> In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. The n-type semiconductor material of the present disclosure is In formula (n1), A 1 and A 2 are each independently a group represented by formula (a-1), P is represented by formula (n2), In formula (n2), Ar 4 and Ar 6 each independently contains a thiophene ring, and Ar 5 is a structure represented by formula (n3), In formula (n3), X 2 is formula (Z-1), formula (Z-4), or formula (Z-6), and Ar 7 and Ar8 is a thiophene ring, a thienothiophene ring, or a cyclopentadithiophene ring, and it is preferred that c and d are 0, or c is 0 and d is 1.

[0293] Specific examples of suitable n-type semiconductor materials represented by formula (n1) of the present disclosure include compounds represented by the following formula:

[0294] [ka]

[0295] [ka]

[0296] [ka]

[0297] [ka]

[0298] (thin film optical absorption edge wavelength (λth)) In one embodiment of the present disclosure, the n-type semiconductor material of the present disclosure preferably has a light absorption edge wavelength (λth) of 1350 nm or more in a thin film including the n-type semiconductor material. A photoelectric conversion element containing the n-type semiconductor material of the present disclosure can perform photoelectric conversion with light having a wavelength of 1350 nm or longer, which is longer than conventional light. From the viewpoint of utilizing light with a long wavelength, the optical absorption end wavelength (λth) is preferably a long wavelength. The optical absorption end wavelength is preferably 1353 nm or longer, more preferably 1360 nm or longer, even more preferably 1370 nm or longer, and particularly preferably 1380 nm or longer.

[0299] The light absorption end wavelength is expressed as the wavelength value at the end of the light absorption wavelength range on the long wavelength side. In the present disclosure, the numerical value of the optical absorption terminal wavelength is specifically expressed by a value determined by the following method.

[0300] The light absorption wavelength is measured using a spectrophotometer that operates in the ultraviolet, visible, and near-infrared wavelength regions (for example, the Varian UV-Visible-Near-Infrared Spectrophotometer "Cary5E"). First, the absorption spectrum of the substrate to be used for measurement is measured. The substrate used may be a quartz substrate, a glass substrate, or the like. Next, a solution containing an n-type semiconductor material or a melt containing an n-type semiconductor material is placed on the substrate to form a thin film containing an n-type semiconductor material. When forming a film from a solution, the film is dried after formation. Then, the absorption spectrum of the laminate of the thin film and the substrate is obtained. The difference between the absorption spectrum of the laminate of the thin film and the substrate and the absorption spectrum of the substrate is obtained as the absorption spectrum of the thin film.

[0301] The absorption spectrum of the thin film is shown with the absorbance of the n-type semiconductor material on the vertical axis and the wavelength on the horizontal axis. It is desirable to adjust the thickness of the thin film so that the absorbance of the largest absorption peak is about 0.4 to 2.

[0302] The optical absorption end wavelength can be determined from the intersection of the first and second reference lines shown below.

[0303] -First Reference Line- The absorbance at the absorption peak point (maximum value) closest to the longest wavelength in the entire absorption waveform (absorption spectrum) is taken as 100%.

[0304] Of the two intersections where the absorption waveform intersects with a line parallel to the horizontal axis (wavelength axis) showing 50% absorbance of the absorption peak point, the intersection located closer to the longer wavelength side than the absorption peak point is defined as the first point.

[0305] Of the two intersections where the absorption waveform intersects with a line parallel to the wavelength axis showing an absorbance of 44% of the absorption peak point, the intersection located closer to the longer wavelength side than the absorption peak point is defined as the second point. The straight line connecting the first point and the second point is defined as the first reference line.

[0306] -Second Reference Line- The absorbance at the absorption peak point (maximum value) closest to the longest wavelength in the entire absorption waveform is taken as 100%.

[0307] Of the two intersections between the absorption waveform and a line parallel to the wavelength axis showing 20% ​​of the absorbance of the absorption peak point, the wavelength of the intersection point that is longer than the absorption peak point is taken as the reference point, and the point on the absorption waveform that is 200 nm longer than the reference point wavelength is taken as the third point. Furthermore, the point on the absorption waveform that is 250 nm longer than the reference point wavelength is taken as the fourth point. The line connecting the third and fourth points is taken as the second reference line.

[0308] The wavelength value at the intersection of the first reference line and the second reference line is defined as the optical absorption terminal wavelength.

[0309] <Other n-type semiconductor materials> The composition of the present disclosure may contain an n-type semiconductor material other than the n-type semiconductor material of the present disclosure described above. Other examples of low molecular weight compounds that can be included as n-type semiconductor materials 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.

[0310] Other examples of polymer compounds that can be included as n-type semiconductor materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having 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, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof.

[0311] The other n-type semiconductor material may be a fullerene derivative.

[0312] Here, the fullerene derivative is fullerene (C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene and C 84 It refers to a compound in which at least a part of a fullerene (C) is modified. In other words, it refers to a compound having one or more groups added to the fullerene skeleton. Hereinafter, C 60 Fullerene derivatives are called "C 60 "Fullerene derivatives" and C 70 Fullerene derivatives are called "C 70 They are sometimes called "fullerene derivatives."

[0313] The fullerene derivative that can be included as another n-type semiconductor material is not particularly limited as long as it does not impair the objective of the present disclosure.

[0314] C that can be contained as other n-type semiconductor materials 60 Specific examples of fullerene derivatives include the following compounds.

[0315] [ka]

[0316] Above C 60 In the formula of the fullerene derivative, the definition of R is as described in paragraph number

[0203] of WO 2023 / 100844. When there are multiple R, the multiple R may be the same or different.

[0317] C 70 Examples of fullerene derivatives include the following compounds:

[0318] [ka]

[0319] <Mass ratio> The mass ratio of the "p-type semiconductor material" to the "n-type semiconductor material" in the composition of the present disclosure 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.

[0320] <Ink> The composition of the present disclosure preferably further contains a solvent and is an ink. The composition of the present disclosure can be used as an ink, and hereinafter the composition will also be referred to as an ink. The ink of the present disclosure 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.

[0321] According to the ink of the present disclosure, by containing the p-type semiconductor material and n-type semiconductor material 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, the manufacturing process of a photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device, thereby improving heat resistance.

[0322] 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.

[0323] 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.

[0324] <First solvent> The first solvent is preferably a solvent capable of dissolving p-type and n-type semiconductor materials, and is preferably an aromatic hydrocarbon.

[0325] Examples of aromatic hydrocarbons include toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), chloroform, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, trimethylbenzene (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1-chloronaphthalene, bromobenzene, tetralin, and indane.

[0326] 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.

[0327] The first solvent is preferably one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, chloroform, 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, chloroform, 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.

[0328] <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, 1-chloronaphthalene, tetralin, 2-isopropylphenol, 2-isopropyl-5-methylanisole, and bromobenzene.

[0329] The second solvent is preferably, for example, acetophenone, propiophenone, 1-chloronaphthalene, butyl benzoate, or methyl benzoate, from the viewpoint of further reducing dark current.

[0330] <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, o-dichlorobenzene and methyl benzoate, chloroform and 1-chloronaphthalene, and trimethylbenzene and 1,2-dimethoxybenzene, and more preferably combinations of tetralin and butyl benzoate, o-dichlorobenzene and 1,2-dimethoxybenzene, chloroform and 1-chloronaphthalene, and trimethylbenzene and 1,2-dimethoxybenzene.

[0331] <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.

[0332] <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.

[0333] 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.

[0334] 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.

[0335] 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.

[0336] 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.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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).

[0342] The conditions for mixing the first and second solvents with the p-type and n-type semiconductor materials are not particularly limited, and may be, for example, mixed at 30° C. to 150° C. for 10 minutes to 24 hours.

[0343] <Photoelectric conversion element> The photoelectric conversion element of the present disclosure preferably includes an anode, a cathode, and an active layer disposed between the anode and the cathode and formed using the composition of the present disclosure. Preferred aspects of the p-type semiconductor material and the n-type semiconductor material contained in the composition are as described above.

[0344] 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.

[0345] Here, an example of a configuration that the photoelectric conversion element of the present disclosure can take will be described. Figure 2 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure.

[0346] 2, the 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.

[0347] 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.

[0348] Components that can be included in the photoelectric conversion element of the present disclosure will be specifically described below.

[0349] <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.

[0350] 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.

[0351] <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.

[0352] 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.

[0353] 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.

[0354] <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.

[0355] 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.

[0356] <Middle class> As shown in FIG. 2, 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.

[0357] 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)).

[0358] As shown in Fig. 2, 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.

[0359] 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.

[0360] 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.

[0361] 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.

[0362] 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.

[0363] As shown in Figure 2, 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.

[0364] 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.

[0365] 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.

[0366] 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).

[0367] 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.

[0368] 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.

[0369] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0370] <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.

[0371] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0372] 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.

[0373] 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.

[0374] <Dark current> In the photoelectric conversion element obtained using the composition of the present disclosure, it is preferable that the dark current is low. 2 Preferably less than 50,000 nA / cm 2 Less than 10,000nA / cm is more preferable. 2 Less than 5,000 nA / cm is more preferable. 2 Less than 1,000 nA / cm is more preferable. 2 The lower limit of the dark current is not particularly limited, and is, for example, 0 nA / cm 2 is.

[0375] In the present disclosure, the dark current is measured by the following method. (1) Sample preparation A glass substrate on which a thin film of ITO (anode) is formed to a thickness of 45 nm by sputtering is prepared, and this glass substrate is subjected to ozone UV treatment as a surface treatment.

[0376] Next, the cleaned glass substrate is spin-coated with a solution of 80% ethoxylated polyethyleneimine aqueous solution (Sigma-Aldrich, 37% by mass aqueous solution) diluted 500 times with water to form a coating film, which is then placed on a hot plate and dried in air at 100°C for 15 minutes to form an electron transport layer.

[0377] Next, the ink to be measured is applied onto the electron transport layer by spin coating to form a coating film, which is then dried by heating for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake process), and then heated for 10 minutes at 100°C on a hot plate in a nitrogen atmosphere (post-bake process) to form an active layer.

[0378] Next, a molybdenum oxide (MoO3) layer is formed on the formed active layer to a thickness of about 30 nm to serve as a hole transport layer.

[0379] Next, a silver (Ag) layer is 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 is manufactured on the glass substrate.

[0380] Next, a UV-curable sealant is applied to the periphery of the glass substrate serving as the sealing substrate, and the glass substrate serving as the sealing substrate is attached to the center of the glass substrate serving as the support substrate. After this, UV light is irradiated 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 has a planar shape of 2 mm x 2 mm when viewed from the thickness direction. The resulting sealed element is used as a sample.

[0381] (2) Dark current measurement For the manufactured sample, a voltage of -10V to 5V is applied to the sealed body of the photodetector element in a dark state where no light is irradiated, and the current value when a bias voltage of -3V is applied, measured using a known method, is obtained as the dark current value.

[0382] <Applications of photoelectric conversion elements> The photoelectric conversion element of the present disclosure can be used in applications such as photodetection elements and solar cells. 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.

[0383] 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 plurality of photoelectric conversion elements can be integrated to form a solar cell module.

[0384] 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.

[0385] 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.

[0386] 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.

[0387] <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.

[0388] (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.

[0389] (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.

[0390] (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.

[0391] 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.

[0392] 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.

[0393] 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.

[0394] 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).

[0395] 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.

[0396] 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 step of the electron transport layer more convenient, it is preferable to form the electron transport layer by any conventionally known suitable vacuum evaporation method.

[0397] (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 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.

[0398] (Step of forming the encapsulant) In forming the encapsulant, any conventionally known 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 them together 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.

[0399] <Photo-detection element> The photoelectric conversion element of the present disclosure, particularly a 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

[0400] Examples are shown below to explain the present disclosure in more detail. The present disclosure is not limited to the examples described below.

[0401] A photoelectric conversion element was fabricated using a p-type semiconductor material and an n-type semiconductor material.

[0402] <p-type semiconductor material> (Synthesis of polymer compound P-1) First, Compound 1 and Compound 2 were synthesized by the method described in Japanese Patent No. 6070722.

[0403] [ka]

[0404] Compound 3 was synthesized by the method described in Chemistry of Materials (2019), 31(3), 919-926.

[0405] [ka]

[0406] Next, compound 1 (0.15 mmol), compound 2 (0.150 mmol), compound 3 (0.300 mmol), water (57.8 g), a 40% by weight potassium phosphate aqueous solution (3.16 mL), THF (37 mL), tetralin (18 mL), and bis(tri-tert-butylphosphine)palladium (0) (0.05 mmol) were added as raw materials to a glass reaction vessel equipped with a cooling device at room temperature and stirred at 65 ° C. for 1 hour. A mixed solution of phenylboric acid (6 mmol) and a 40% by weight potassium phosphate aqueous solution (0.3 mL) was added as raw materials to the reaction vessel and stirred at 65 ° C. for 1 hour. The resulting organic layer was washed with an aqueous sodium diethyldithiocarbamate solution, acetic acid water, and water, and the washed organic layer was added to methanol and the precipitated solid was filtered to recover the crude polymer. The obtained crude polymer was dissolved in tetralin and passed through 5B (JIS P 3801: Type 5B) filter paper, and then added to methanol again. The precipitated solid was collected by filtration to obtain polymer compound P-1.

[0407] [ka]

[0408] (Synthesis of polymer compounds P-2 and P-3) The polymer compound P-2 and the polymer compound P-3 were synthesized by referring to the method described in ACS Appl. Mater. Interfaces 2021, 13, 56420-56429.

[0409]

Chemical formula

[0410]

Chemical formula

[0411] (Polymer compound PCE-10) PCE-10 was purchased from Ossila.

[0412]

Chemical formula

[0413] <n-type semiconductor material> (Synthesis of compound N-1) Compound N-1 was synthesized by referring to the method described in U.S. Patent Application Publication No. 2023 / 0094427.

[0414]

Chemical formula

[0415] (Synthesis of compound N-2) Compound 5 was synthesized using compound 4.

[0416]

Chemical formula

[0417] Compound 4 was synthesized by referring to the method described in International Publication No. 2014 / 112656. Compound 4 (1.00 g, 12.7 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.934 g, 29.3 mmol) (JiangSu GR-Chem Co., Ltd.), and tetrahydrofuran (THF, 9 g) were charged into a 100 mL three-neck flask and nitrogen was bubbled through for 30 min. Pd2(dba)3 (0.058 g, 0.06 mmol), P(tBu3)HBF4 (0.037 g, 0.13 mmol), and 3 mol / L K3PO4 aqueous solution (2.36 g) were then added in that order, and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature (25°C), diluted with toluene, washed twice with water, dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration, after which the total amount was concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / toluene = 80 / 20 to 0 / 100 (mass ratio)) to obtain 0.53 g (41% yield) of compound 5 as a blue-purple solid. The NMR spectrum of the obtained compound 5 was analyzed. The results are as follows. 1 H-NMR (300MHz,CHLOROFORM-D) δ 9.75 (2H), 7.46 (2H), 7.09 (1H), 6.99 (1H), 4.09 (4H), 1.78-1.95 (m, 6H), 1.22-1.64 (m, 56H), 0.84-1.02 (m, 18H)

[0418] Compound 5 was used to synthesize compound N-2. [ka]

[0419] Compound 5 (0.266 g, 0.264 mmol), the above compound 5-2 (0.194 g, 0.793 mmol), synthesized according to the method described in International Publication No. 2020 / 109823, p-TsOH·HO (0.151 g, 0.0793 mmol), EtOH (2.4 g), toluene (5.3 g), and MgSO (0.13 g) were charged into a 30 mL three-neck flask 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. After concentrating the mixture using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100% by mass) to obtain 0.265 g (72% yield) of compound N-2 as a blue-green-black solid. The NMR spectrum of the obtained compound N-2 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.96 (1H) , 8.78 (2H), 8.67 (1H), 8.17 (2H), 7.54 (1H), 7.46 (2H), 7.13 (1H), 4.24 (4H), 1.94-2.05 (m, 6H), 1.23-1.76 (m, 56H), 0.84-1.12 (m, 18H)

[0420] (Synthesis of Compound N-3) Compound 7 was synthesized using compound 6.

[0421] [ka]

[0422] 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 temperature was raised 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 completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane = 100% by mass) to obtain 13.4 g of compound 7 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 7 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)

[0423] Compound 8 was synthesized using compound 7.

[0424] [ka]

[0425] A 1 L four-neck flask was charged with compound 7 (15.4 g, 47.3 mmol) and THF (461 g). The atmosphere was replaced 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, the mixture was quenched by pouring in a 3% by weight aqueous solution of sodium sulfite (249 g). After warming 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: hexane = 100% by weight) to obtain 18.5 g of compound 8 as a colorless, transparent liquid.

[0426] Compound 9 was synthesized using compound 8.

[0427] [ka]

[0428] A 50 mL four-neck flask was charged with compound 8 (18.5 g, 45.9 mmol) and THF (185 g). The atmosphere was purged with nitrogen and then cooled to -73 °C. LDA (1 M in THF / hexane, 45.9 mL, 45.9 mmol) was added and the mixture was kept at -73 °C for 2 hours. DMF (7.1 mL, 91.9 mmol) was slowly added, and the mixture was warmed to room temperature and stirred for 2 hours. After quenching by adding 20% ​​aqueous ammonium chloride solution (98 mL), the aqueous layer was separated from the resulting mass, 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: hexane / ethyl acetate = 70 / 1 (volume ratio)) to obtain 5.26 g of compound 9 as a yellow liquid. The NMR spectrum of the resulting compound 9 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.70 (1H), 7.37 (1H), 3.95 (2H), 1.80-1.74 (1H), 1.49-1.27 (m, 24H), 0.90-0.86 (m, 6H)

[0429] Compound 11 was synthesized using compound 10.

[0430] [ka]

[0431] 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., 0.477 g, 1.18 mmol), bis(pinacolato)diboron (0.752 g, 3.0 mmol), [Ir(OMe)(cod)]2 (9 mg, 0.01 mmol), and tBu-bpy (8 mg, 0.02 mmol). After purging with nitrogen, 7 g of cyclohexane was added and the flask was placed in an oil bath heated to 60°C to maintain the temperature. After stirring for 2 hours, 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 while passing the mixture through silica gel, and then completely concentrated using a rotary evaporator to obtain 0.802 g of crude compound 11.

[0432] Compound 12 was synthesized using compound 11 and compound 9.

[0433] [ka]

[0434] Crude compound 11 (3.36 g), compound 9 (5.09 g, 11.8 mmol), and THF (30.2 g) were charged into a 100 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.235 g, 0.257 mmol), P(tBu3)HBF4 (0.149 g, 0.513 mmol), and 3 mol / L K3PO4 aqueous solution (9.50 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 to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 30 / 1 (volume ratio)) to obtain 3.28 g of compound 12 as a red viscous liquid.

[0435] Compound 12 was used to synthesize compound N-3.

[0436] [ka]

[0437] A 200 mL four-neck flask was charged with compound 12 (3.28 g, 2.97 mmol), compound 5-2 (2.18 g, 8.91 mmol), p-TsOH·HO (1.70 g, 8.91 mmol), EtOH (29.5 g), toluene (65.6 g), and MgSO (1.64 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% by mass) to obtain 3.41 g (74% yield) of compound N-3 as a blue-green-black solid. NMR spectroscopy of the resulting compound N-3 was performed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.01 (2H), 8.80 (2H), 8.17 (2H), 7.74 (2H), 7.54 (2H), 4.19 (4H), 2.01-1.95 (m, 6H), 1.58-0.63 (m, 90H)

[0438] (Synthesis of Compound N-4) Compound N-4 was synthesized with reference to the method described in JP-A-2023-107154.

[0439] [ka]

[0440] (Synthesis of Compound N-5) Compound 14 was synthesized using compound 13.

[0441] [ka]

[0442] 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 14.

[0443] Compound 15 was synthesized using compound 7.

[0444] [ka]

[0445] A 200 mL four-neck flask was charged with compound 7 (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 crude compound 15. The NMR spectrum of the resulting compound 15 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)

[0446] Compound 16 was synthesized using compound 15.

[0447] [ka]

[0448] Crude compound 15 (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 subjected to nitrogen bubbling 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 aqueous K3PO4 solution (60.6 g) were added in that order, and the mixture was heated 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 16 as a yellow-brown liquid. The NMR spectrum of the obtained compound 16 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)

[0449] Compound 17 was synthesized using compound 16.

[0450] [ka]

[0451] A 100 mL four-neck flask was charged with compound 16 (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 17 as a yellow-brown liquid. The NMR spectrum of the resulting compound 17 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)

[0452] Compound 18 was synthesized using compound 14 and compound 17.

[0453] [ka]

[0454] Crude compound 14 (1.13 g), compound 17 (1.80 g, 2.81 mmol), and THF (18.2 g) were charged into a 50 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.0560 g, 0.0612 mmol), P(tBu3)HBF4 (0.0372 g, 0.128 mmol), and 3 mol / L K3PO4 aqueous solution (5.66 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 = 8 / 1 (volume ratio)) to obtain 1.19 g of compound 18 as a dark red viscous 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 (2H), 7.46 (2H), 7.20 (2H), 7.13 (2H), 4.10 (4H), 4.06 (2H), 1.94-0.61 (m, 126H)

[0455] Compound 18 was used to synthesize compound N-5.

[0456] [ka]

[0457] A 100 mL four-neck flask was charged with compound 18 (1.15 g, 0.754 mmol), compound 5-2 (0.553 g, 2.26 mmol), p-TsOH·HO (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), and MgSO (0.575 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% by mass) to obtain 0.890 g (60% yield) of compound N-5 as a black solid. NMR spectra of the resulting compound N-5 were analyzed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.94-8.93 (m, 2H), 8.69 (2H), 8.10 (2H), 7.50-7.35 (m, 6H), 4.19-4.15 (m, 8H), 1.94-0.64 (m, 126H)

[0458] <ΔE H-H Calculation of> Compounds N-1 to N-5 were each divided into an electron-withdrawing monovalent group A and a divalent group P other than an electron-withdrawing monovalent group. Compound I was a compound in which a hydrogen atom was bonded to the bond between group A and group P, and Compound II was a compound in which a hydrogen atom was bonded to each bond between group P and group A. The absolute value of the difference between the HOMO energy of compound I and the HOMO energy of compound II (ΔE H-H ) was calculated. Compounds N-1 to N-5 are compounds represented by APA, that is, compounds represented by A in formula (n1) of the present disclosure. 1 and A 2 Therefore, the HOMO energy of compound Ia and the HOMO energy of compound Ib in compounds N-1 to N-5 are the same value, and are regarded as the HOMO energy of compound I.

[0459] The HOMO energy was calculated using the quantum chemistry calculation program Gaussian 03, with the ground state structure optimized by the density functional method at the B3LYP level, and 6-31g* as the basis function. In calculating the HOMO energy, the alkyl group contained in compound II was selected from the propyl group (-CH2-CH2-CH3) as a representative example. The calculated values ​​for the compound before and after the alkyl group was changed to a propyl group are almost the same.

[0460] [Table 1]

[0461] [Table 2]

[0462] The absolute value of the difference between the HOMO energy of the corresponding compound I and the HOMO energy of compound II (ΔE H-H ) was calculated. Compound N-1:3.81eV Compound N-2: 3.75eV Compound N-3:3.77eV Compound N-4:2.71eV Compound N-5:3.95eV

[0463] <Ink Preparation> [Preparation of Ink (I-1)] The following components were mixed and stirred for 1 hour at 50° C. The resulting mixture was filtered using a filter to obtain ink (I-1). P-type semiconductor material: polymer compound P-3...0.34% by mass N-type semiconductor material: Compound N-1...0.29% by mass N-type semiconductor material: C60PCBM...0.12% by mass Solvent: Chloroform / 1-chloronaphthalene = 99.5% by mass / 0.5% by mass ... remaining amount to make 100% by mass of the entire ink

[0464] 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.

[0465] [Preparation of Ink (I-2)] The following components were mixed and stirred for 1 hour at 100° C. The resulting mixture was filtered using a filter to obtain ink (I-2). P-type semiconductor material: polymer compound P-2...0.45% by mass N-type semiconductor material: Compound N-1...0.48% by mass n-type semiconductor material: C60PCBM...0.20 mass% Solvent: Chlorobenzene...the remaining amount that makes up 100% of the total ink mass

[0466] [Preparation of Ink (I-3)] 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-3). P-type semiconductor material: polymer compound P-3...0.34% by mass N-type semiconductor material: Compound N-2...0.29% by mass N-type semiconductor material: C60PCBM...0.12% by mass Solvent: Chloroform / 1-chloronaphthalene = 98% by mass / 2% by mass ... remaining amount to make 100% by mass of the total ink

[0467] [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-4). P-type semiconductor material: polymer compound P-1...2.20% by mass N-type semiconductor material: Compound N-3...2.2% by mass Solvent: Trimethylbenzene / 1,2-dimethoxybenzene = 97% by mass / 3% by mass...the remaining amount that makes up 100% of the total ink

[0468] [Preparation of Ink (I-5)] 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-5). P-type semiconductor material: polymer compound P-1...2.20% by mass N-type semiconductor material: Compound N-3...1.54 mass% N-type semiconductor material: C60PCBM...0.66 mass% Solvent: Trimethylbenzene / 1,2-dimethoxybenzene = 97% by mass / 3% by mass...the remaining amount that makes up 100% of the total ink

[0469] [Preparation of Ink (I-6)] The following components were mixed and stirred for 1 hour at 100° C. The resulting mixture was filtered using a filter to obtain ink (I-6). P-type semiconductor material: polymer compound PCE-10...0.45% by mass N-type semiconductor material: Compound N-1...0.48% by mass n-type semiconductor material: C60PCBM...0.20 mass% Solvent: Chlorobenzene...the remaining amount that makes up 100% of the total ink mass

[0470] PCE-10 (Poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) manufactured by 1-material was purchased from the market and used.

[0471] [Preparation of Ink (I-7)] 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-7). P-type semiconductor material: polymer compound P-3...0.34% by mass N-type semiconductor material: Compound N-4...0.41% by mass Solvent: Chloroform / 1-chloronaphthalene = 98% by mass / 2% by mass ... remaining amount to make 100% by mass of the total ink

[0472] [Preparation of Ink (I-8)] 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-3...0.34% by mass N-type semiconductor material: Compound N-5...0.41% by mass Solvent: Chloroform / 1-chloronaphthalene = 98% by mass / 2% by mass ... remaining amount to make 100% by mass of the total ink

[0473] [Preparation of Ink (I-9)] The following components were mixed and stirred for 4 hours at 60° C. The resulting mixture was filtered using a filter to obtain ink (I-9). ·P-type semiconductor material: polymer compound P3HT...1.50% by mass N-type semiconductor material: Compound N-1...1.26% by mass N-type semiconductor material: C60PCBM...0.54 mass% Solvent: Orthodichlorobenzene...the remaining amount that makes up 100% of the total ink mass

[0474] P3HT (Poly(3-hexylthiophene-2,5-diyl)) was a commercially available product manufactured by Sigma-Aldrich and was used.

[0475] [Preparation of Ink (I-10)] 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-10). P-type semiconductor material: polymer compound PCE-10...1.20% by mass N-type semiconductor material: Compound N-3...1.2% by mass Solvent: Trimethylbenzene / 1,2-dimethoxybenzene = 97% by mass / 3% by mass...the remaining amount that makes up 100% of the total ink

[0476] Example 1 [Production of photoelectric conversion element and its encapsulated body] A glass substrate on which a thin film of ITO (anode) 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.

[0477] Next, the cleaned glass substrate was spin-coated with a solution of 80% ethoxylated polyethyleneimine aqueous solution (Sigma-Aldrich, 37% by mass aqueous solution) diluted 500 times with water to form a coating film, which was then placed on a hot plate and dried in air at 100°C for 15 minutes to form an electron transport layer.

[0478] 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 using a hot plate heated to 70°C in the atmosphere (pre-bake process), and then heated for 10 minutes at 100°C on a hot plate in a nitrogen atmosphere (post-bake process) to form an active layer.

[0479] 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.

[0480] 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.

[0481] 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.

[0482] <Example 2, Example 3, Comparative Examples 1 to 4> Inks (I-2), (I-3), and (I-6) to (I-9) were used instead of ink (I-1), and samples 2, 3, and 6 to 9 were obtained in the same manner as in Example 1 already described.

[0483] <Example 4, Example 5, Comparative Example 5> As in Example 1, a zinc oxide dispersion was applied to a cleaned glass substrate by spin coating to form a coating film, and the substrate was then placed on a hot plate and dried in the atmosphere at 120°C for 10 minutes to form an electron transport layer.

[0484] After the active layer formation process, Samples 4, 5, and 10 were obtained in the same manner as in Example 1, except that Inks (I-4), (I-5), and (I-10) were used instead of Ink (I-1).

[0485] That is, the ink compositions and dissolution conditions in each of the examples and comparative examples are as shown in Table 3 below.

[0486] <Active layer film thickness> The film thicknesses of the active layers of the photoelectric conversion elements formed in Samples 1 to 10 are as shown in Table 3 below.

[0487] <Evaluation of photoelectric conversion elements (dark current)> For the manufactured sample 1, in the dark state without light irradiation, a voltage from -10V to 5V was applied to the encapsulation of the photodetector element, and the current value when a bias voltage of -3V measured using a known method was taken as the value of the dark current. The results are shown in Table 3 below.

[0488] <Evaluation of the photoelectric conversion element> With a bias voltage of -3V applied to the obtained photoelectric conversion element, using a spectral sensitivity measuring device (manufactured by Spectrometer Co., Ltd., product name: CEP-25SC type), monochromatic light of 1300 nm (photon number: 1×10 14 ) was irradiated onto the photoelectric conversion element, the generated current value was measured, and a photodiode drive test was carried out by a known method. In this test, when the photoelectric conversion effect was confirmed, it was determined as having OPD power generation, and when there was no photoelectric conversion, it was determined as having no OPD power generation. The results are shown in Table 3 below.

[0489]

Table 3

[0490] <Evaluation of the LUMO of the p-type semiconductor material> The HOMO energy (eV) and LUMO energy (eV) of the polymer compounds P-1 to P-3, PCE-10, and P3HT were calculated based on the values measured by ultraviolet photoelectron spectroscopy (UPS method). Hereinafter, the calculation method will be specifically described.

[0491] (1) Sample preparation First, polymer compounds P-1, PCE-10, and P3HT were each dissolved in orthodichlorobenzene at 1.0 mass% to obtain solutions. Next, each of the obtained solutions was applied onto a glass substrate by the spin coating method to form a coating film, and dried on a hot plate at 70°C to form a layer with a thickness of 100 nm as a sample.

[0492] Polymer compounds P-2 and P-3 were each dissolved in orthodichlorobenzene at 0.5% by mass to obtain a solution, which was then applied to a glass substrate by spin coating to form a coating film, which was then dried on a hot plate at 70°C to form a layer with a thickness of 100 nm, which was used as a sample.

[0493] (2) Measurement of HOMO energy and calculation of LUMO energy by UPS method For each of the obtained samples, the HOMO energy of each of the polymer compounds P-1 to P-3, PCE-10, and P3HT can be calculated based on the number of electrons measured in air by the UPS method using a photoelectron spectrometer (Model AC-2, manufactured by Riken Keiki Co., Ltd.).

[0494] The LUMO energy of each of the polymer compounds P-1 to P-3, PCE-10, and P3HT can be calculated by the following formula. Formula: LUMO energy = band gap (Eg) - HOMO energy

[0495] Here, the band gap (Eg) can be calculated using the following formula based on the absorption edge wavelength of the p-type semiconductor material. Formula: Band gap (Eg) = hc / absorption edge wavelength In the formula, h represents Planck's constant (h = 6.626 × 10 -34 Js), c represents the speed of light (c=3×10 8 m / s).

[0496] The absorption edge wavelength was measured using a spectrophotometer capable of measuring in the wavelength regions of ultraviolet, visible, and near-infrared light (for example, an ultraviolet-visible-near-infrared spectrophotometer Cary5E manufactured by Agilent).

[0497] In the absorption spectrum obtained by a spectrophotometer, i.e., the absorption spectrum plotted with the absorbance (absorption intensity) of the compound on the vertical axis and the wavelength on the horizontal axis, the absorption edge wavelength (nm) was defined as the wavelength value at the intersection of the baseline and a straight line fitted to the shoulder (high wavelength side) of the absorption peak.

[0498] The calculated LUMO energies are shown in Table 5 below.

[0499] [Table 4]

[0500] As described above, in Examples 1 to 5, the dark current in the photoelectric conversion element was suppressed, and it was possible to absorb light of long wavelengths. [Explanation of symbols]

[0501] 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. comprising a p-type semiconductor material and an n-type semiconductor material; The p-type semiconductor material includes a structural unit X represented by the following formula: and a structural unit Y which is a divalent group and has a chemical structure different from that of the structural unit X, the LUMO energy of the p-type semiconductor material is −3.35 eV or more and −2.75 eV or less; 【Chemical 1】 (In the structural unit X, Ar １ and Ar ３ each independently represents an optionally substituted trivalent aromatic carbocyclic group or an optionally substituted trivalent aromatic heterocyclic group, Ar ２ each independently represents an optionally substituted tetravalent aromatic carbocyclic group or an optionally substituted tetravalent aromatic heterocyclic group, n is an integer from 0 to 3. The n-type semiconductor material is a compound represented by the following formula (n1): A １ -P-A ２ (n1) (In formula (n1), A １ and A ２ are each independently an electron-withdrawing monovalent group, and P is a divalent group having a structure represented by the following formula (n2): Group A １ The compound Ia is a compound in which a hydrogen atom is bonded to the bond to the group P of the formula Ib. ２ The compound Ib is a compound in which a hydrogen atom is bonded to the bond to the group P. １ and group A ２ wherein compound II is a compound in which a hydrogen atom is bonded to each bond of compound Ia and compound II, and the absolute value of the difference in HOMO energy between compound Ia and compound II and the absolute value of the difference in HOMO energy between compound Ib and compound II are both 2.75 eV or more and 3.90 eV or less. 【Chemistry 2】 (In formula (n2), Ar ４ ~Ar ６ each independently represents a divalent aromatic carbocyclic group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent.

2. In the structural unit X, Ar １ ~Ar ３ 2. The composition according to claim 1, wherein at least one of the groups is an aromatic heterocyclic group containing at least one of a sulfur atom and a nitrogen atom.

3. 2. The composition according to claim 1, wherein the structural unit X has a structure represented by the following formula (X1): 【Chemistry 3】 (In formula (X1), n ​​is an integer of 0 to 3.)

4. Ar in formula (n2) ５ The composition according to claim 1 or claim 2, wherein is a structure represented by the following formula (n3): 【Chemistry 4】 (In formula (n3), X ２ represents a divalent group, Ar ７ and Ar ８ each independently represent an optionally substituted fused or non-fused trivalent aromatic carbocyclic group, or an optionally substituted fused or non-fused trivalent aromatic heterocyclic group, c and d are each independently 0 or 1.

5. 3. The composition according to claim 1 or claim 2, 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 (I), a structural unit represented by the following formula (II), and a structural unit represented by the following formula (III): 【Chemistry 5】 (In formula (I), Ar ９ and Ar 10 represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents a group represented by the following formula (Z-1) to formula (Z-7). 【Chemistry 6】 In formulas (Z-1) to (Z-7), R １ 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, cyano group, nitro group, -C(=O)-R Ｙ or a group represented by -SO ２ -R Ｚ represents a group represented by R Ｙ and R Ｚ are each independently hydrogen atoms, an alkyl group which may have a substituent, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted aryloxy group, or represents an optionally substituted monovalent heterocyclic group, R １ If there are two R １ may be the same or different. In formula (II), Ar 11 represents an optionally substituted divalent monocyclic aromatic carbocyclic group or an optionally substituted divalent monocyclic aromatic heterocyclic group. In formula (III), Ar 12 and Ar 13 each independently represents an aromatic carbocyclic group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and m represents an integer of 1 or more.

6. The composition according to claim 1 or 2, further comprising a solvent, and is in the form of an ink.

7. A photoelectric conversion element comprising: an anode; a cathode; and an active layer provided between the anode and the cathode and formed using the composition according to claim 1 or 2.

8. The photoelectric conversion element according to claim 7 , which is a photodetector element.

9. An optical sensor comprising the photoelectric conversion element according to claim 8 .

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