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

Abstract

To provide a compound for absorbing light of a long wavelength, a composition, an ink, a photoelectric conversion element, and an optical sensor.SOLUTION: There is provided a compound represented by formula (1). In formula (1), D includes two or more aromatic rings that are fused or linked and represents a divalent group having four or more double bonds included in a conjugate structure which connects a bond between D and p1 and a bond between D and p2 at the minimum distance, p1 and p2 represent divalent groups, at least one of p1 and p2 is a divalent group including at least one unit represented by formula (TZ), and each A independently represents an electron-withdrawing monovalent group. In the formula (TZ), * is a bond with the D side in formula (1), ** is a bond with the A side in formula (1), and X1 is an electron donor group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] 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 a compound used in a photoelectric conversion element, for example, an NFA (Non-Fullerene Acceptor) having a specific structure as described in Patent Document 1 is known. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2023 / 038064 Summary of the Invention [Problem to be solved by the invention]

[0005] However, knowledge about compounds that enable photoelectric conversion in the SWIR (Short Wavelength Infrared) region, particularly in the eye-safe wavelength range of 1300 nm to 1400 nm, which is a long wavelength, is currently limited.

[0006] The present disclosure has been made in view of the above, and relates to providing a compound, composition, ink, photoelectric conversion element, and optical sensor that absorb long wavelength light. [Means for solving the problem]

[0007] Specific means for solving the above problems include the following aspects. <1> A compound represented by the following formula (1):

[0008] [ka]

[0009] (In formula (1), D represents a divalent group containing two or more fused or linked aromatic rings, and containing four or more double bonds in the conjugated structure connecting the bond between D and p1 and the bond between D and p2 in the shortest distance; p1 and p2 represent a divalent group, and at least one of p1 and p2 is a divalent group containing at least one unit represented by the following formula (TZ), and p1 and p2 may be the same or different: Each A independently represents an electron-withdrawing monovalent group.

[0010] [ka]

[0011] In the formula (TZ), * represents a bond to the D side in formula (1), and ** represents a bond to the A side in formula (1), X1 represents an electron-donating group. <2> p1 or p2 is a divalent group containing at least one unit represented by formula (TZ). <1> The compound described in <3> Represented by the following formula (2): <1> The compound described in

[0012] [ka]

[0013] (In formula (2), D and two A's are linked to each other via a thiazole ring substituted with an electron-donating group X1; D represents a divalent group containing two or more fused or linked aromatic rings, and having four or more double bonds in a conjugated structure connecting two bonds between D and the two thiazole rings at the shortest distance; Each A independently represents an electron-withdrawing monovalent group. <4> X1 is independently -R TZ , -OR TZ , -NR TZ 2, and -SR TZ is an electron-donating group selected from the group consisting of R TZ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic; <1> ~ <3> 1. The compound according to any one of claims 1 to 9. <5> D is any structure selected from the group consisting of the following formulas (D-1) to (D-4): <1> ~ <4> 1. The compound according to any one of claims 1 to 9.

[0014] [ka]

[0015] (In formula (D-1) and formula (D-2), X is any of the groups represented by the following formulas (X-1) to (X-6).

[0016] [ka]

[0017] In formula (D-3), formula (D-4), and formula (X-1) to formula (X-6), R d are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In formula (D-2), Ar 1 and Ar 2 are each independently an aromatic carbocyclic ring which may have a substituent and which may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and which may be further condensed with a plurality of ring structures. <6> Each A is independently any one of groups represented by the following formulas (a-1) to (a-5): <1> ~ <5> 1. The compound according to any one of claims 1 to 9.

[0018] [ka]

[0019] (In the above formulas (a-1) to (a-5), 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 multiple substituents, the multiple substituents may be the same or different. X 4 , X 5 , and X 6 are each independently an oxygen atom, a sulfur atom, an alkylidene group, ═C(—CN)2, or ═C(—CN)—CR a represents a group represented by R a represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic. <7> The semiconductor material includes a p-type semiconductor material and an n-type semiconductor material, <1> ~ <6> A composition comprising a compound according to any one of claims 1 to 4. <8> The p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): <7> The composition described in

[0020] [ka]

[0021] (In formula (3), Ar 3 and Ar 4each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7).

[0022] [ka]

[0023] In formulas (Z-1) to (Z-7), R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different, In formula (4), Ar 5 represents a divalent aromatic heterocyclic group. <9> <1> ~ <6> An ink comprising the compound according to any one of the above items and a solvent. <10> an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material; The n-type semiconductor material is <1> ~ <6> A photoelectric conversion element comprising the compound according to any one of the above items. <11> A photodetector element, <10> The photoelectric conversion element according to claim 1. <12> <10> or <11> An optical sensor comprising the photoelectric conversion element according to claim 1. [Effects of the Invention]

[0024] According to the present disclosure, there are provided a compound, composition, ink, photoelectric conversion element, and optical sensor that absorb long wavelength light. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element. DETAILED DESCRIPTION OF THE INVENTION

[0026] 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.

[0027] 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.

[0028] 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.

[0029] The following describes commonly used terms in this disclosure. In the description of this disclosure, the following descriptions apply unless otherwise specified.

[0030] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0031] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0032] "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 %.

[0033] 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.

[0034] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0035] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0036] In the present disclosure, "side chain A" refers to hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or nitro group, This means that

[0037] In the present disclosure, "side chain B" refers to the group options in the above "side chain A" excluding hydrogen atoms.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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."

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] "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.

[0083] "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.

[0084] "Substituted oxysulfonyl group" means -(SO2)-OR X or -O-(SO2)-R X where R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] Examples of the substituted cycloalkynyl group include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0097] 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.

[0098] The symbol "*" that may be added to a chemical formula represents a bond. A dotted line in a chemical formula also represents a bond. When a chemical formula contains two symbols "*" or two dotted lines, there is no particular limitation as to which of the two units to which the "*" and dotted line are bonded.

[0099] "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.

[0100] The ink may be a solution or a dispersion such as an emulsion or suspension.

[0101] 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.

[0102] "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.

[0103] ≪Compound≫ The compound of the present disclosure is represented by the following formula (1):

[0104] [ka]

[0105] In formula (1), D represents a divalent group containing two or more fused or linked aromatic rings, and containing four or more double bonds in the conjugated structure connecting the bond between D and p1 and the bond between D and p2 in the shortest distance; p1 and p2 represent a divalent group, and at least one of p1 and p2 is a divalent group containing at least one unit represented by the following formula (TZ), and p1 and p2 may be the same or different: Each A independently represents an electron-withdrawing monovalent group.

[0106] [ka]

[0107] In the formula (TZ), * represents a bond to the D side in formula (1), and ** represents a bond to the A side in formula (1), X1 represents an electron-donating group.

[0108] The compounds of the present disclosure absorb light at longer wavelengths. The action of the compounds of the present disclosure is not clear, but is presumed as follows.

[0109] In the formula (1), which represents a compound of the present disclosure, the group represented by p1 and the group represented by p2 are each a linker, the group represented by D is a core, and the group represented by A is each an acceptor. In addition, in the compound of the present disclosure, a ring structure having two bonds (which may be either a monocyclic structure or a condensed ring structure) included in the chemical structure of the main skeleton that connects two A's in the shortest way is taken as one unit each. In addition, in the compound of the present disclosure, the "bond to the D side" may be a bond directly bonded to D or a bond bonded to D through another chemical structure. Similarly, the "bond to the A side" may be a bond directly bonded to A or a bond bonded to A through another chemical structure.

[0110] In formula (1), at least one of p1 and p2 is a divalent group containing at least one unit represented by formula (TZ). The main skeleton of the unit represented by formula (TZ) is a thiazole ring. And in formula (TZ), * is the bond to the D side in formula (1), and ** is the bond to the A side in formula (1). That is, the nitrogen atom of the thiazole ring in formula (TZ) has a great influence on the acceptor in terms of the distribution of the LUMO orbital, and since it reduces the electron density on the acceptor side, the energy level of the LUMO in the compound becomes low. Furthermore, since the electron-donating group X1 in formula (TZ) has a great influence on the core in terms of the distribution of the HOMO orbital, it increases the electron-donating property (that is, core property) of the core, and the energy level of the HOMO in the compound becomes high. From the above, the HOMO-LUMO gap as a compound molecule of the present disclosure becomes small, and the compound of the present disclosure can absorb light with a long wavelength. Note that the present disclosure is not limited to the above estimation mechanism at all.

[0111] <p1 and p2; Linkers connecting A and D> [Formula (TZ)] In formula (1), at least one of p1 and p2 is a divalent group containing at least one unit represented by formula (TZ) below, and p1 and p2 may be the same or different.

[0112] [ka]

[0113] In the formula (TZ), * represents a bond to the D side in formula (1), and ** represents a bond to the A side in formula (1), X1 represents an electron-donating group.

[0114] From the viewpoint of increasing the wavelength, it is preferable that p1 or p2 (that is, only one of p1 and p2) is a divalent group containing at least one unit represented by formula (TZ). From the viewpoint of ease of synthesis, it is also preferred that both of p1 and p2 are divalent groups containing at least one unit represented by formula (TZ).

[0115] From the viewpoint of increasing the wavelength, p1 and p2 are each preferably a divalent group containing 1 to 3 units represented by formula (TZ), more preferably a divalent group containing 1 to 2 units, and even more preferably a divalent group containing 1 unit. From the viewpoint of increasing the wavelength, p1 and p2 are each preferably a divalent group in which 1 to 3 units represented by formula (TZ) are linked together, more preferably a divalent group in which 1 to 2 units are linked together, and even more preferably a divalent group in which one unit is linked together. From the viewpoint of ease of synthesis, it is also preferable that p1 and p2 are each independently a divalent group having one unit represented by formula (TZ), as in the compound of the present disclosure represented by formula (2) described below.

[0116] (X1) In formula (TZ), each X1 is independently -R TZ , -OR TZ , -NR TZ 2, and -SRTZ It is preferable that the group is an electron donating group selected from the group consisting of: R TZ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic. From the viewpoint that compounds tend to absorb light of long wavelengths, R TZ are each independently preferably an alkyl group having 1 to 40 carbon atoms or an aryl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 1 to 30 carbon atoms, and even more preferably an alkyl group having 1 to 20 carbon atoms.

[0117] (Example of a unit represented by formula (TZ)) Examples of formula (TZ) include groups represented by the following formulae: In each formula, * represents a bond to the D side in formula (1), ** represents a bond to the A side in formula (1), and *** represents a bond to the parent skeleton shown at the top.

[0118] [ka]

[0119] [Units other than those expressed by formula (TZ)] In formula (1), p1 and p2 may contain a unit represented by a formula other than (TZ). The unit represented by a formula other than (TZ) that may be contained in p1 and p2 is not particularly limited and may be a monocyclic or fused ring having two bonds, and the number of double bonds contained in the conjugated structure connecting the two bonds in the unit by the shortest distance may be two, three, or four to six.

[0120] (Ar p (units expressed as In formula (1), units other than those represented by formula (TZ) that may be included in p1 and p2 include a divalent aromatic ring Ar p It is preferable that the compound contains Ar. p If there are multiple Ar p may be the same or different from each other.

[0121] For example, in compounds of the present disclosure, p1 comprises the formula (TZ) and Ar p and p2 is a divalent group having the formula (TZ) and Ar p It may be a divalent group containing at least one of the following. Alternatively, for example, in the compounds of the present disclosure, p1 is of formula (TZ) and Ar p and p2 is a divalent group containing at least one of the formula (TZ) and Ar p It may be a divalent group which may contain:

[0122] Ar p The chemical structure of is not particularly limited as long as the effects of the present disclosure are achieved. Ar p As the ring structure, a divalent aromatic carbocyclic group which may have a substituent and may further have a condensed ring structure, or a divalent aromatic heterocyclic group which may have a substituent and may further have a condensed ring structure is preferred.

[0123] The divalent aromatic carbocyclic group and the divalent aromatic heterocyclic group preferably have three or less double bonds in the main chain, that is, the conjugated structure connecting two bonds in the shortest distance. 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.

[0124] Ar p 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.

[0125] {Ar pa divalent aromatic carbocyclic group represented by the formula: Ar p Specifically, the divalent aromatic carbocyclic group (arylene group) represented by the following formula (I) specifically means the atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. Here, the aromatic hydrocarbon also includes compounds having fused rings in which multiple ring structures are fused together.

[0126] Ar p 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.

[0127] Ar p Examples of divalent aromatic carbocyclic groups represented by the formula include divalent aromatic carbocyclic groups represented by the formula below. The divalent aromatic carbocyclic groups represented by the formula below may further have a substituent. In the formula, the symbol "*" indicates a bond, and there is no particular limitation as to whether the bond is to the D side or the A side in formula (1).

[0128] [ka]

[0129] {Ar p a divalent aromatic heterocyclic group represented by the formula: Ar p 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.

[0130] Ar p Examples of divalent aromatic heterocyclic groups represented by the formula include divalent aromatic heterocyclic groups represented by the formula below. These groups may further have a substituent. In the formula, the symbol "*" indicates a bond, and there is no particular limitation as to whether the bond is to the D side or the A side in formula (1).

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] Ar p 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.

[0135] [ka]

[0136] {Ar p Substituents in Ar p Examples of the substituent that the divalent aromatic carbocyclic group and divalent aromatic heterocyclic group substituent 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.

[0137] Ar pThe substituents that the divalent aromatic carbocyclic group and divalent aromatic heterocyclic group substituent represented by the formula (I) may have are each independently preferably an alkyl group, cycloalkyl group, aryl group, alkyloxy group, cycloalkyloxy group, aryloxy group, substituted amino group, or substituted oxycarbonyl group, which may have a substituent, more preferably an alkyl group, aryl group, alkyloxy group, substituted amino group, or substituted oxycarbonyl group, and even more preferably an alkyl group, alkyloxy group, or substituted oxycarbonyl group.

[0138] From the viewpoint that compounds tend to absorb light of long wavelengths, Ar p When A has a substituent, the substituent adjacent to D is preferably an electron-donating group. The substituent adjacent to D means the substituent in p1 or p2 that is closest to D among the substituents on the molecular chain connecting A and D in the shortest distance (if the molecular chain includes a ring structure, the substituents on the ring structure).

[0139] {Preferable examples of divalent aromatic heterocyclic groups} Ar represented by the above formula p Preferred examples of the divalent aromatic heterocyclic group represented by the formula include divalent groups represented by the following formula: In the formula, the symbol "*" indicates a bond, and there is no particular limitation as to whether the bond is to the D side or the A side in formula (1).

[0140] [ka]

[0141] [Examples of p1 and p2] In the above, p1, p2, formula (TZ), and Ar p The preferred embodiments of p1 and p2 have been described above, but the combination of each of the preferred embodiments results in more preferred embodiments of p1 and p2. From the viewpoint that the compound easily absorbs light of a long wavelength, when p1 and p2 have a unit represented by formula (TZ), they are each preferably any of the groups represented by formulas (TZ-1) to (TZ-4) below, more preferably any of the groups represented by formulas (TZ-1) to (TZ-3) below, and even more preferably a group represented by formula (TZ-1) below. In order for the compound to easily absorb light of a long wavelength, when p1 and p2 do not have a unit represented by formula (TZ), they each independently represent a unit represented by the following formula (Ar p -1)~(Ar p -2) is preferred.

[0142] In addition, the following formulas (TZ-1) to (TZ-4) and formula (Ar p -1)~(Ar p -2) In X1 and Ar p The definitions, examples, and preferred embodiments of are as described above. When a plurality of X1s are present in the formula, the X1s may have the same structure or may be different from each other. When a plurality of Ar p If exists, Ar p may have the same structure or may be different. *1 is the bond to the D side, and ** is the bond to the A side.

[0143] [ka]

[0144] From the viewpoint that the compound easily absorbs light of long wavelengths, when the compound has a unit represented by formula (TZ), p1 and p2 are preferably each independently any of the groups represented by the following formulas. In the following formulas, *1 is a bond to the D side, and ** is a bond to the A side. *** is a bond to the parent skeleton shown on the left side. In (TZ-4), multiple X1 may have the same structure or may be different from each other.

[0145] [ka]

[0146] In view of the ease with which the compound absorbs light of a long wavelength, when the compound does not have a unit represented by formula (TZ), p1 and p2 are preferably each independently any of the groups represented by the following formulas. In the following formulas, *1 represents a bond to the D side, and ** represents a bond to the A side. (Ar p -2) In the middle, there are multiple Ar p may have the same structure or may be different from each other. p exists and Ar p When multiple examples are listed, any of the Ar in the parent skeleton p But, Ar p There is no particular limitation on which of the above examples is used, and all combinations are included as preferred embodiments.

[0147] [ka]

[0148] [Formula (2)] The compound of the present disclosure is preferably represented by the following formula (2):

[0149] [ka]

[0150] In formula (2), D and two A's are linked to each other via a thiazole ring substituted with an electron-donating group X1 (i.e., formula (TZ) in formula (1)), D represents a divalent group containing two or more fused or linked aromatic rings, and having four or more double bonds in a conjugated structure connecting two bonds between D and the two thiazole rings at the shortest distance; Each A independently represents an electron-withdrawing monovalent group.

[0151] The explanations of D, A, and X1 in formula (2) are the same as the explanations of D, A, and X1 in formula (1), including definitions, examples, preferred embodiments, etc.

[0152] <D;コア> In the compound represented by formula (1) of the present disclosure, D represents a divalent group containing two or more fused or linked aromatic rings, and containing four or more double bonds in the conjugated structure connecting the bond between D and p1 and the bond between D and p2 in the shortest distance. In the compound represented by formula (2) of the present disclosure, D represents a divalent group containing two or more fused or linked aromatic rings, and having four or more double bonds contained in the conjugated structure connecting the two bonds between D and the two thiazole rings in the shortest distance. In the present disclosure, the explanation of D in formula (1) is the same as the explanation of D in formula (2), including definitions, examples, preferred embodiments, and the like.

[0153] In D, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is 4 or more. From the viewpoint of facilitating absorption of long-wavelength light, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is preferably 4 to 12, more preferably 4 to 8, even more preferably 4 to 6, still more preferably 4 or 5, and even more preferably 4.

[0154] From the viewpoint that the compound easily absorbs light of a long wavelength, D is preferably a donor group (also referred to as a group with donating properties).

[0155] [Fused ring] D is preferably a fused ring, and more preferably a polycyclic aromatic group having two bonds (that is, a divalent polycyclic aromatic group). The polycyclic aromatic group in D may be either a polycyclic aromatic heterocyclic group or a polycyclic aromatic carbocyclic group, and is preferably a polycyclic aromatic heterocyclic group from the viewpoint of absorbing light of long wavelengths. The heteroatom in the polycyclic aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, more preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a nitrogen atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the polycyclic aromatic group in D preferably has a sulfur-containing heterocycle, and more preferably is a sulfur-containing heterocyclic group.

[0156] (Example of a fused ring) From the viewpoint that the compound easily absorbs light of a long wavelength, D is preferably any structure selected from the group consisting of the following formulae (D-1) to (D-4), and more preferably a group represented by the following formula (D-1) or formula (D-2). In the following formulas (D-1) to (D-4), the symbol "*" represents a bond to p1 or p2 in formula (1), or a bond to the thiazole ring in formula (2). There is no particular limitation as to which of p1 or p2 the two symbols "*" represent, or which of the two thiazole rings they represent.

[0157] [ka]

[0158] In formula (D-1) and formula (D-2), X is any of the groups represented by the following formulas (X-1) to (X-6): In formulas (X-1) to (X-6), the dotted lines indicate bonds to formula (D-1) or formula (D-2).

[0159] [ka]

[0160] In formulas (X-1) to (X-6), R deach independently represents "side chain A". In formula (D-2), Ar 1 and Ar 2 are each independently an aromatic carbocycle which may have a substituent and which may be further condensed with a plurality of ring structures, or an aromatic heterocycle which may have a substituent and which may be further condensed with a plurality of ring structures.

[0161] Since it is preferable that the polycyclic aromatic group in D has a side chain, in the formulas (X-1) to (X-6), a plurality of R d At least one of these is preferably not a hydrogen atom.

[0162] In each of the formulas (X-1) to (X-6), R d If there are two, then two R d may be the same or different from each other. From the viewpoint that the compound easily absorbs light of a long wavelength, X is preferably any of the groups represented by formula (X-1) to formula (X-4), and more preferably a group represented by formula (X-1). In formulas (X-1) to (X-6), R d are each independently preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group, which may have a substituent, more preferably an alkyl group or an aryl group, which may have a substituent, and even more preferably an alkyl group.

[0163] In formula (D-2), Ar 1 and Ar 2 are each independently an aromatic carbocycle which may have a substituent and which may be further condensed with a plurality of ring structures, or an aromatic heterocycle which may have a substituent and which may be further condensed with a plurality of ring structures.

[0164] Ar 1 and Ar 2The 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.

[0165] Ar 1 and Ar 2 The aromatic heterocycles that can constitute the above may each be a single ring or a fused ring. When the aromatic heterocycle is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the rings may be fused rings having aromaticity. When these rings have multiple substituents, these substituents may be the same or different.

[0166] Ar 1 and Ar 2 Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0167] Ar 1 and Ar 2 Specific examples of aromatic heterocycles that can constitute the above include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0168] In formula (D-3) and formula (D-4), R d The definition and preferred embodiments of R in the above formulas (X-1) to (X-6) are as follows: d In formula (D-3), two R dmay be the same or different from each other.

[0169] [Two or more linked aromatic rings] D is also preferably two or more aromatic rings linked by a single bond. The aromatic ring may be a single ring or a fused ring. The aromatic ring may be either an aromatic carbocyclic group or an aromatic heterocyclic group, and is preferably an aromatic heterocyclic group from the viewpoint of absorbing long wavelength light. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, more preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a nitrogen atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the aromatic ring in D preferably contains a sulfur-containing heterocycle, and more preferably is a sulfur-containing heterocycle.

[0170] From the viewpoint of absorbing light of long wavelengths, the two or more linked aromatic rings are preferably two to five linked aromatic rings, more preferably two to three linked aromatic rings, and even more preferably two linked aromatic rings.

[0171] (Example of two or more linked aromatic rings) From the viewpoint that the compound easily absorbs light of a long wavelength, D is also preferably a structure represented by the following formula (D-5). In the following formula (D-5), the symbol "*" represents a bond to p1 or p2 in formula (1), or a bond to the thiazole ring in formula (2). Note that there is no particular limitation as to which of p1 or p2, or which of the two thiazole rings, the two symbols "*" represent.

[0172] [ka]

[0173] In formula (D-5), R d each independently represents "side chain A".

[0174] Since the aromatic ring in D preferably has a side chain, in formula (D-5), d At least one of these is preferably not a hydrogen atom.

[0175] In formula (D-5), two R d may be the same or different from each other. In formula (D-5), R d are each independently preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group, which may have a substituent, more preferably an alkyl group or an aryl group, which may have a substituent, and even more preferably an alkyl group.

[0176] [Side chain] In D, the fused ring or the two or more linked aromatic rings preferably have a side chain. In the present disclosure, the side chain refers to a group that substitutes a hydrogen atom bonded to an atom that constitutes the main skeleton (single ring or fused ring, etc.). In D, the side chain is preferably "side chain B".

[0177] In D, the side chain preferably has an aromatic ring or a branched chain, and more preferably has a branched chain. In D, the fused ring or the two or more linked aromatic rings may have multiple side chains, and when multiple side chains are present, the multiple side chains may be the same or different from each other.

[0178] In D, when a plurality of side chains are present, each side chain is preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group, which may have a substituent, and more preferably a cycloalkyl group.

[0179] In D, the side chain preferably has 6 or more carbon atoms, more preferably 6 to 30 carbon atoms, even more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0180] The atom in D to which the side chain is bonded is preferably an sp3 carbon, sp3 silicon, sp2 carbon, or sp2 silicon, more preferably an sp3 carbon or sp2 carbon, and even more preferably an sp3 carbon from the viewpoint of absorbing light of a long wavelength. When the side chain is bonded to the sp3 carbon, the side chain protrudes perpendicularly to the π plane of the aromatic ring structure containing the sp3 carbon in the main skeleton, which promotes association between molecules of the compound of the present disclosure.

[0181] [Example of D] Examples of formula (D-1) include groups represented by the following formulae (d-1-1) to (d-1-3). Examples of formula (D-2) include groups represented by the following formulae (d-2-1) to (d-2-10). Examples of formula (D-3) include groups represented by the following formulae (d-3-1) to (d-3-4). Examples of formula (D-4) include groups represented by the following formulae (d-4-1) to (d-4-2).

[0182] In the formula, R d1 If there are multiple R d1 may be the same or different. d1 The definitions of each are independently the same as those of R d is the same as the definition of In the formulas (d-2-1) to (d-2-10), each U is independently S, SiR d1 2, Se, NR d1 or O. Preferably, U is S. In the formula, the symbol "*" represents a bond to p1 or p2 in formula (1), or a bond to the thiazole ring in formula (2). There is no particular limitation as to which of p1 or p2 the two symbols "*" represent, or which of the two thiazole rings they represent.

[0183] From the viewpoint that the compound easily absorbs light of long wavelengths, D is It is preferably a group represented by formula (d-1-1), formula (d-1-3), formula (d-2-1) to formula (d-2-3), formula (d-3-3) to formula (d-3-4), or formula (d-4-2), It is more preferable that the group is represented by formula (d-1-1), formula (d-2-2) to formula (d-2-3), or formula (d-3-4), More preferably, it is a group represented by formula (d-1-1), formula (d-2-3), or formula (d-3-4).

[0184] [ka]

[0185] [ka]

[0186] [ka]

[0187] [ka]

[0188] Specific examples of D include groups represented by the following formulae. In each formula, the symbol "*" indicates a bond to p1 or p2 in formula (1), or a bond to the thiazole ring in formula (2). There are no particular restrictions on which of the two symbols "*" are a bond to p1 or p2, or a bond to which of the two thiazole rings. *** indicates a bond to the parent skeleton shown on the left side of each symbol. In the formula, R d1 When there are multiple R groups, they may have the same structure or different structures. d1 exists and R d1 If multiple examples of R are listed, d1 But R d1There is no particular limitation on which of the above examples is used, and all combinations are included as preferred embodiments.

[0189] [ka]

[0190] [ka]

[0191] <A;アクセプター> In the compounds of the present disclosure, in formula (1) and formula (2), A each independently represents an electron-withdrawing monovalent group. In the present disclosure, the explanation of A in formula (1) is the same as the explanation of A in formula (2), including definitions, examples, preferred embodiments, and the like.

[0192] In formula (1) and formula (2), each of the two A's may be the same group or different groups. From the viewpoint of facilitating the synthesis of the compound of the present disclosure, each of the two A's in formula (1) and formula (2) is preferably the same group.

[0193] From the viewpoint that the compound easily absorbs light of a long wavelength, in formula (1) and formula (2), A is preferably each independently any of the groups represented by the following formulas (a-1) to (a-5), and more preferably a group represented by formula (a-1). In the formulas, the symbol "*" indicates a bond to p1 or p2 in formula (1) or a bond to the thiazole ring in formula (2).

[0194] [ka]

[0195] (T) In the above formulas (a-1) to (a-5), 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 multiple substituents, the multiple substituents may be the same or different.

[0196] 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.

[0197] Examples of the heterocycle represented by T which may have a substituent include aromatic heterocycles, preferably aromatic heterocycles. 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.

[0198] 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.

[0199] (X 4 , X 5 , X 6 ) X 4 , X 5 , and X 6 are each independently an oxygen atom, a sulfur atom, an alkylidene group, ═C(—CN)2, or ═C(—CN)—CR a X represents a group represented by the formula: 4 , X 5 , and X 6 are preferably each independently an oxygen atom or =C(-CN)2.

[0200] R a represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic.

[0201] (Example A) In the above, preferred embodiments of T, X 4 , X 5 , and X 6 Preferred embodiments of the formula: a The preferred embodiments of the present invention have been described above, but a combination of each of the preferred embodiments results in a more preferred embodiment of the present invention. Examples of A include groups represented by the following formulae (a-1-1) to (a-1-22), (a-2-1), (a-2-2), and (a-3-1). In each formula, the symbol "*" indicates a bond to p1 or p2 in formula (1), or a bond to the thiazole ring in formula (2).

[0202] From the viewpoint that the compound easily absorbs light of a long wavelength, in formula (1) and formula (2), A is preferably each independently a group represented by the following formula (a-1-1), (a-1-6), (a-1-7), (a-1-14), (a-1-15) or (a-1-16), more preferably a group represented by the following formula (a-1-1), (a-1-15) or (a-1-16), and even more preferably a group represented by the following formula (a-1-1).

[0203] [ka]

[0204] [ka]

[0205] In formulas (a-1-1) to (a-1-22), (a-2-1), (a-2-2), and (a-3-1), R a1 ~R a9 each independently represents a hydrogen atom or a substituent. R a1 ~R a9 are preferably each independently a hydrogen atom, a halogen atom, a cyano group, a straight-chain alkyl group, a branched alkyl group, a silyl group, an ester group, an alkyloxy group, a thioalkyl group, a haloalkyl group, an alkene group, an alkyne group, a cyano-substituted alkyl group, a nitro-substituted alkyl group, a hydroxy-substituted alkyl group, or a keto-substituted alkyl group, more preferably each independently a hydrogen atom, a halogen atom, an alkyloxy group, a cyano group, or an alkyl group, and even more preferably each independently a hydrogen atom, a fluorine atom, a chlorine atom, or a cyano group.

[0206] The linear alkyl group preferably has 1 to 30 carbon atoms, the branched alkyl group preferably has 3 to 30 carbon atoms, the silyl group preferably has 1 to 30 carbon atoms, the ester group preferably has 2 to 30 carbon atoms, the alkyloxy group preferably has 1 to 30 carbon atoms, the thioalkyl group preferably has 1 to 30 carbon atoms, the haloalkyl group preferably has 1 to 30 carbon atoms, the alkene group preferably has 2 to 30 carbon atoms, the alkyne group preferably has 2 to 30 carbon atoms, the cyano-substituted alkyl group preferably has 2 to 30 carbon atoms, the nitro-substituted alkyl group preferably has 1 to 30 carbon atoms, the hydroxy-substituted alkyl group preferably has 1 to 30 carbon atoms, and the keto-substituted alkyl group preferably has 3 to 30 carbon atoms.

[0207] Examples of A include groups represented by the following formulae: In each formula, the symbol "*" indicates a bond to p1 or p2 in formula (1), or a bond to the thiazole ring in formula (2).

[0208] [ka]

[0209] <Specific Examples of Compounds of the Present Disclosure> In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. The compounds of the present disclosure are represented by formula (1): D is any one of the groups represented by formula (D-1) to formula (D-4), At least one of p1 and p2 independently has the formula (TZ), Each A is preferably independently a group represented by formula (a-1).

[0210] The compounds of the present disclosure are represented by formula (1): D is any one of groups represented by formula (d-1-1) to formula (d-1-3), p1 and p2 each independently have the formula (TZ), wherein X1 is -R TZ group or -ORTZ It is the basis, It is more preferable that each A is independently a group represented by formula (a-1-1) or (a-1-16).

[0211] More specific examples of preferred compounds of the present disclosure include compounds represented by the following formulas:

[0212] [ka]

[0213] <Energy difference (Eg) between the energy level of the lowest exciton singlet state of a compound and the energy level of the ground state> The compound of the present disclosure preferably has an energy difference (Eg) between the energy level of the lowest exciton singlet state and the energy level of the ground state calculated by a computational science method of 1.55 eV or less. The computational science method may be, for example, a method of calculation using a quantum chemistry calculation program.

[0214] Using the quantum chemistry calculation program Gaussian 03, the ground state structure is optimized using density functional theory 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 (Eg).

[0215] When the energy band gap of the compound is 1.55 eV or less, when the compound of the present disclosure is used in a photoelectric conversion element, photoelectric conversion at longer wavelengths is easily achieved.

[0216] The energy band gap of the compound is more preferably 1.50 eV or less, even more preferably 1.45 eV or less, and particularly preferably 1.40 eV or less. The lower limit of the energy band gap of the compound is not particularly limited, but is, for example, 0.75 eV. In one embodiment of the present disclosure, the energy band gap of the compound is preferably 0.75 eV to 1.55 eV.

[0217] <Wavelength λ corresponding to the energy band gap Eg > In one embodiment of the present disclosure, the compounds of the present disclosure have an energy bandgap corresponding to a wavelength λ Eg It is preferable that the calculated value according to density functional theory is 800 nm or more.

[0218] In one embodiment of the present disclosure, the compounds of the present disclosure have an energy bandgap corresponding to a wavelength λ Eg The wavelength λ corresponding to the energy band gap is more preferably 850 nm or more, and even more preferably 870 nm or more, from the viewpoint that the compound is likely to absorb light of a long wavelength. Eg The upper limit of the calculated value by density functional theory is not particularly limited, but is preferably 1650 nm or less, more preferably 1400 nm or less, and even more preferably 1200 nm or less. Eg The calculated value of the wavelength range according to density functional theory is preferably 800 nm to 1650 nm.

[0219] wavelength λ Eg The calculated value of by density functional theory is obtained from the energy band gap (Eg) obtained above and the following (Equation 1). λ Eg = 1240 / Eg (Equation 1)

[0220] <Light absorption edge wavelength of thin film (λth)> The compound of the present disclosure preferably has a light absorption terminal wavelength (λth) of 1400 nm or more when formed into a thin film from the compound. A photoelectric conversion element containing the compound of the present disclosure is more likely to perform photoelectric conversion in light with a longer wavelength than conventional elements. From the viewpoint of utilizing light with a longer wavelength, the optical absorption terminal wavelength (λth) is preferably a longer wavelength. The optical absorption terminal wavelength is preferably 1400 nm or more, more preferably 1450 nm or more, even more preferably 1500 nm or more, and even more preferably 1530 nm or more. The upper limit of the optical absorption terminal wavelength is not particularly limited, but may be, for example, 2000 nm or less, 1950 nm or less, 1900 nm or less, or 1850 nm or less. In one embodiment of the present disclosure, the optical absorption terminal wavelength is preferably 1400 nm to 2000 nm.

[0221] 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.

[0222] The measurement sample was prepared as follows. The compound is added to orthodichlorobenzene to a concentration of 1.0% by mass. The mixture is heated and stirred for 4 hours at 65°C under a nitrogen atmosphere to prepare a solution. The filtrate from the solution is used as the coating solution. The coating solution is placed on a glass substrate whose surface has been cleaned with UV-ozone, and a film is formed by spin coating. The spin-coated coating film is placed on a hot plate. It is then dried under atmospheric conditions at 70°C for 5 minutes to obtain a thin film for UV-Vis spectrum measurement.

[0223] The light absorption wavelength is measured using a spectrophotometer that operates in the ultraviolet, visible, and near-infrared wavelength regions (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian).

[0224] The absorption spectrum of a thin film is shown with the absorbance of the compound 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.

[0225] The optical absorption end wavelength can be determined from the intersection of the first and second reference lines shown below.

[0226] -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%.

[0227] 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.

[0228] Of the two intersections between the absorption waveform and 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.

[0229] -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%.

[0230] 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 50 nm longer than the reference point wavelength is taken as the third point. Also, the point on the absorption waveform that is 100 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.

[0231] The wavelength value at the intersection of the first reference line and the second reference line is defined as the optical absorption terminal wavelength.

[0232] <Maximum absorption wavelength of solution (λmax)> The compound of the present disclosure preferably has a maximum absorption wavelength (λmax) of 970 nm or longer when formed into a solution. A photoelectric conversion element containing the compound of the present disclosure is more likely to perform photoelectric conversion in light with a longer wavelength than conventional elements. From the viewpoint of utilizing light with a longer wavelength, the maximum absorption wavelength (λmax) is preferably a longer wavelength. The maximum absorption wavelength is more preferably 980 nm or longer, even more preferably 990 nm or longer, and even more preferably 1000 nm or longer. The upper limit of the maximum absorption wavelength is not particularly limited, but may be, for example, 1800 nm or shorter, 1700 nm or shorter, 1600 nm or shorter, or 1500 nm or shorter. In one embodiment of the present disclosure, the maximum absorption wavelength is preferably 900 nm to 1800 nm.

[0233] The maximum absorption wavelength of a solution is expressed as the wavelength value of the absorption peak wavelength. In the present disclosure, the maximum absorption wavelength of a solution is specifically represented by a value determined by the following method.

[0234] The measurement sample was prepared as follows. A compound is added to orthodichlorobenzene to a concentration of 0.025% by mass to prepare a stock solution, which is then diluted 20 times with orthodichlorobenzene to obtain a solution (concentration: 0.00125% by mass) for UV-Vis spectrum measurement.

[0235] The light absorption wavelength is measured using a spectrophotometer that operates in the ultraviolet, visible, and near-infrared wavelength regions (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian).

[0236] The absorption spectrum of a solution is shown with the absorbance of the compound on the vertical axis and the wavelength on the horizontal axis. It is desirable to adjust the concentration of the solution so that the absorbance of the largest absorption peak is around 0.4 to 2.

[0237] Among the absorption peaks of the absorption spectrum measured in the wavelength range of 300 nm to 2000 nm, the absorption peak point (maximum value) closest to the longest wavelength is taken as the value of the maximum absorption wavelength.

[0238] ≪Composition≫ The composition of the present disclosure includes a p-type semiconductor material and an n-type semiconductor material, and as the n-type semiconductor material, it is preferable to include the compound of the present disclosure.

[0239] The composition of the present disclosure may contain components other than the p-type semiconductor material and the n-type semiconductor material. Further, the composition of the present disclosure may contain only the compound of the present disclosure as the n-type semiconductor material, or may contain other compounds other than the compound of the present disclosure. Other compounds that can be included as the n-type semiconductor material may be low molecular weight compounds or high molecular weight compounds.

[0240] <n-type semiconductor material> Examples of the low molecular weight compounds that can be included as the n-type semiconductor material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and phenanthrene derivatives such as bathocuproine.

[0241] Examples of the high molecular weight compounds that can be included as the n-type semiconductor material include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or the main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

[0242] The other compound may also be a fullerene derivative.

[0243] 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."

[0244] The fullerene derivative that can be included as the n-type semiconductor material is not particularly limited as long as it does not impair the objective of the present disclosure.

[0245] C that can be contained as an n-type semiconductor material 60 Specific examples of fullerene derivatives include the following compounds.

[0246] [ka]

[0247] 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.

[0248] C 70 Examples of fullerene derivatives include the following compounds:

[0249] [ka]

[0250] <p-type semiconductor material> The p-type semiconductor material is preferably a polymer compound having a predetermined weight average molecular weight in terms of polystyrene.

[0251] Here, the weight average molecular weight in terms of polystyrene means the weight average molecular weight calculated using a polystyrene standard sample by gel permeation chromatography (GPC).

[0252] The weight average molecular weight in terms of polystyrene of the p-type semiconductor material is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in a solvent.

[0253] The p-type semiconductor material is preferably a π-conjugated polymer compound (also referred to as a D-A type conjugated polymer compound) containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit). Note that which is the donor structural unit or the acceptor structural unit can be relatively determined from the energy levels of HOMO or LUMO.

[0254] Here, the donor structural unit is a structural unit with an excess of π electrons, and the acceptor structural unit is a structural unit lacking π electrons.

[0255] In the present disclosure, the structural units that can constitute the p-type semiconductor material include structural units in which the donor structural unit and the acceptor structural unit are directly bonded, and further include structural units in which the donor structural unit and the acceptor structural unit are bonded via an arbitrarily suitable spacer (group or structural unit).

[0256] Examples of the p-type semiconductor material that is a polymer compound include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and polyfluorene and its derivatives.

[0257] The p-type semiconductor material is preferably a polymer compound containing at least one selected from the group consisting of a constitutional unit represented by the following formula (3) and a constitutional unit represented by the following formula (4). The constitutional unit represented by the following formula (3) is usually preferably a donor constitutional unit. The constitutional unit represented by the following formula (4) is usually preferably an acceptor constitutional unit.

[0258] [ka]

[0259] -Formula (3)- In formula (3), Ar 3 and Ar 4 each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7).

[0260] [ka]

[0261] In formulae (Z-1) to (Z-7), the definition of each R is independently the same as the definition of "side chain A". In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different.

[0262] Ar 3 and Ar 4 The aromatic heterocycle that can constitute the above ring includes not only a single ring and a fused ring in which the heterocycle itself exhibits aromaticity, but also a ring in which an aromatic ring is fused to a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0263] Ar 3 and Ar 4The aromatic heterocycles that can constitute the above may each be a single ring or a fused ring. When the aromatic heterocycle is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the rings may be fused rings having aromaticity. When these rings have multiple substituents, these substituents may be the same or different.

[0264] Ar 3 and Ar 4 Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0265] Specific examples of the aromatic heterocycle include the ring structures of the compounds already described as aromatic heterocyclic compounds, such as an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0266] The constitutional unit represented by formula (3) is preferably a constitutional unit represented by the following formula (3-1), (3-2) or (3-3).

[0267] [ka]

[0268] In formulas (3-1), (3-2) and (3-3), Ar 3 , Ar 4 and R are defined as Ar in formula (3). 3 , Ar4 and the definition of "side chain A".

[0269] Specific examples of suitable structural units represented by formula (3) include structural units represented by the following formulas.

[0270] [ka]

[0271] In the above formula, the definition of R is the same as the definition of "side chain A." When there are two R's, the two R's may be the same or different.

[0272] More specific examples of preferred structural units represented by formula (3) include structural units represented by the following formulas.

[0273] [ka]

[0274] -Formula (4)- In formula (4), Ar 5 represents a divalent aromatic heterocyclic group.

[0275] Ar 5 The divalent aromatic heterocyclic group represented by the following formula (I) preferably has 2 to 60 carbon atoms, more preferably 4 to 60 carbon atoms, and even more preferably 4 to 20 carbon atoms.

[0276] Ar 5 The divalent aromatic heterocyclic group represented by the formula (Ar) may have a substituent. 5Examples of the substituent that the divalent aromatic heterocyclic group represented by the formula (I) may have include a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amide group, an optionally substituted acid imide group, an optionally substituted substituted oxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a cyano group, and a nitro group.

[0277] As the constitutional unit represented by formula (4), constitutional units represented by the following formulae (4-1) to (4-10) are preferred.

[0278] [ka]

[0279] In the formulas (4-1) to (4-10), R is as defined for "side chain A." X 2 and X 3 each independently represents an oxygen atom or a sulfur atom. Z 1 and Z 2 each independently represents a group represented by ═C(R)— or a nitrogen atom. When there are two R's, the two R's may be the same or different.

[0280] X in formulas (4-1) to (4-10) 2 and X 3 are preferably sulfur atoms from the viewpoint of availability of raw material compounds.

[0281] As described above, the structural units represented by formulae (4-1) to (4-10) can generally function as acceptor structural units. However, without being limited thereto, the structural units represented by formulae (4-4), (4-5), and (4-7) in particular can also function as donor structural units.

[0282] The p-type semiconductor material is preferably a π-conjugated polymer compound that includes a structural unit containing a thiophene skeleton and that includes a π-conjugated system.

[0283] Ar 5 Specific examples of the divalent aromatic heterocyclic group represented by the formula (101) to the formula (191) described in paragraphs

[0255] to

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

[0284] The polymer compound that is a p-type semiconductor material is preferably a π-conjugated polymer compound that includes a constitutional unit represented by formula (3) as a donor constitutional unit and a constitutional unit represented by formula (4) as an acceptor constitutional unit.

[0285] In a polymer compound that is a p-type semiconductor material, the polymer compound that is a p-type semiconductor material may contain, as a structural unit, a structure in which the structural unit represented by formula (3) and the structural unit represented by formula (4) already explained are linked together.

[0286] The polymer compound that is a p-type semiconductor material may contain two or more types of constitutional units represented by formula (3), or may contain two or more types of constitutional units represented by formula (4).

[0287] For example, from the viewpoint of improving solubility in a solvent, the polymer compound that is a p-type semiconductor material may contain a constitutional unit represented by formula (IV) described in paragraphs

[0263] to

[0277] of WO 2023 / 100844.

[0288] The constitutional unit represented by formula (IV) is preferably a constitutional unit represented by the following formula (IV-1) or formula (IV-2).

[0289] [ka]

[0290] In formula (IV-1) and formula (IV-2), the definition of R is the same as the definition of "side chain A." The two Rs may be the same or different.

[0291] The structural unit constituting the polymer compound that is a p-type semiconductor material may be a structural unit in which two or more structural units selected from the above structural units are combined and linked together.

[0292] When a polymer compound serving as a p-type semiconductor material contains a constitutional unit represented by formula (3) and / or a constitutional unit represented by formula (4), the total amount of the constitutional unit represented by formula (3) and the constitutional unit represented by formula (4) is usually preferably 20 mol % to 100 mol %, assuming the amount of all constitutional units contained in the polymer compound as 100 mol %. From the viewpoint of improving the charge transport properties as a p-type semiconductor material, it is more preferably 40 mol % to 100 mol %, and even more preferably 50 mol % to 100 mol %.

[0293] Specific examples of polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas (P-1) to (P-19).

[0294] [ka]

[0295] [ka]

[0296] [ka]

[0297] [ka]

[0298] [ka]

[0299] [ka]

[0300] In the above formula, the definition of R is the same as that of "side chain A." Multiple Rs may be the same or different.

[0301] When the polymer compound exemplified above is used as a p-type semiconductor material, it is possible to suppress a decrease in EQE due to heat treatment during a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device, or the like, or to further improve the EQE, thereby improving the heat resistance of the photoelectric conversion element.

[0302] Ink The ink of the present disclosure preferably contains the compound of the present disclosure and a solvent. The ink of the present disclosure also preferably contains the p-type semiconductor material of the present disclosure, the n-type semiconductor material, and a solvent. Since the ink of the present disclosure contains the compound of the present disclosure as the n-type semiconductor material, it is preferably an ink for forming an active layer of a photoelectric conversion element, and more preferably an ink for forming a bulk heterojunction active layer.

[0303] According to the ink of the present disclosure, by containing a p-type semiconductor material and a compound of the present disclosure, it is possible to suppress a decrease in EQE or to further improve the EQE due to heat treatment during, for example, a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device, thereby improving heat resistance.

[0304] 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.

[0305] 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.

[0306] <First solvent> The first solvent is preferably a solvent in which the p-type semiconductor material can be dissolved, and is preferably an aromatic hydrocarbon.

[0307] Examples of aromatic hydrocarbons include toluene, xylenes (e.g., o-xylene, m-xylene, p-xylene), chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, trimethylbenzenes (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzenes (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalenes (e.g., 1-methylnaphthalene), 1-chloronaphthalene, bromobenzene, tetralin, and indane.

[0308] 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.

[0309] The first solvent is preferably one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, and indan, and more preferably toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, mesitylene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, or indan.

[0310] <Second solvent> The second solvent is preferably selected from the viewpoint of facilitating the production process and further improving the properties of the photoelectric conversion element. Examples of the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone; ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate, and benzyl benzoate; ether solvents such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and 1-methoxynaphthalene; 1,2,4-trimethylbenzene, 1,2,4-trichlorobenzene, tetralin, 2-isopropylphenol, 2-isopropyl-5-methylanisole, and bromobenzene.

[0311] The second solvent is preferably, for example, acetophenone, propiophenone, butyl benzoate, or methyl benzoate from the viewpoint of increasing wavelength.

[0312] <Combination of first and second solvents> Examples of suitable combinations of the first solvent and the second solvent include combinations of tetralin and ethyl benzoate, tetralin and propyl benzoate, tetralin and butyl benzoate, o-dichlorobenzene and 1,2-dimethoxybenzene, and o-dichlorobenzene and methyl benzoate, and more preferably combinations of tetralin and butyl benzoate, and o-dichlorobenzene and 1,2-dimethoxybenzene.

[0313] <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.

[0314] <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.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] 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.

[0319] 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.

[0320] 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.

[0321] 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.

[0322] 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.

[0323] 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).

[0324] <Photoelectric conversion element> The photoelectric conversion element of the present disclosure includes an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material, and the n-type semiconductor material preferably includes the compound of the present disclosure. Preferred aspects of the p-type semiconductor material and the n-type semiconductor material are as described above.

[0325] 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.

[0326] Here, an example of a configuration that the photoelectric conversion element of the present disclosure can take will be described. Figure 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure.

[0327] 1, a photoelectric conversion element 10 is provided on a support substrate 11. The photoelectric conversion element 10 includes an anode 12 provided in contact with the support substrate 11, a hole transport layer 13 provided in contact with the anode 12, an active layer 14 provided in contact with the hole transport layer 13, an electron transport layer 15 provided in contact with the active layer 14, and a cathode 16 provided in contact with the electron transport layer 15. In this configuration example, a sealing member 17 is further provided in contact with the cathode 16.

[0328] 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.

[0329] Components that can be included in the photoelectric conversion element of the present disclosure will be specifically described below.

[0330] <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.

[0331] 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.

[0332] <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.

[0333] 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.

[0334] 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.

[0335] <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.

[0336] 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.

[0337] <Middle class> As shown in FIG. 1, the photoelectric conversion element of the present disclosure preferably includes an intermediate layer (buffer layer) such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer) as a component for improving properties such as photoelectric conversion efficiency.

[0338] 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)).

[0339] As shown in Figure 1, the photoelectric conversion element preferably includes a hole transport layer between the anode and the active layer. The hole transport layer has the function of transporting holes from the active layer to the electrode.

[0340] 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.

[0341] 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.

[0342] 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.

[0343] 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.

[0344] As shown in Figure 1, the photoelectric conversion element of the present disclosure preferably includes an electron transport layer as an intermediate layer between the cathode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the cathode. The electron transport layer may be in contact with the cathode. The electron transport layer may be in contact with the active layer.

[0345] 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.

[0346] 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.

[0347] 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).

[0348] 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.

[0349] 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.

[0350] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0351] <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.

[0352] The sealing member may be a sealing layer having a structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0353] 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.

[0354] 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.

[0355] <Applications of photoelectric conversion elements> The photoelectric conversion element of the present disclosure may be used as a photodetector element or a solar cell. The photoelectric conversion element of the present disclosure may be used immediately after production, or may be left to stand or stored after production and then used. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from the transparent or semitransparent electrode side while a voltage (reverse bias voltage) is applied between the electrodes, and can function as a photodetector (photosensor). Furthermore, by integrating a plurality of photodetectors, the element can also be used as an image sensor. Thus, the photoelectric conversion element of the present disclosure can be particularly suitably used as a photodetector.

[0356] Furthermore, the photoelectric conversion element of the present disclosure can generate photovoltaic power between the electrodes when irradiated with light, and can operate as a solar cell. A solar cell module can also be formed by integrating a plurality of photoelectric conversion elements.

[0357] 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.

[0358] 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.

[0359] 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.

[0360] <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.

[0361] (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.

[0362] (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.

[0363] (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.

[0364] 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.

[0365] 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.

[0366] 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.

[0367] 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).

[0368] 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.

[0369] The method for producing a photoelectric conversion element according to the present disclosure includes a step of forming an electron transport layer (electron injection layer) on an active layer. The method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the electron transport layer, it is preferable to form the electron transport layer by any suitable conventional vacuum deposition method.

[0370] (Cathode formation process) The method for forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by, for example, applying the above-exemplified electrode materials to the electron transport layer by any suitable conventional method such as coating, vacuum deposition, sputtering, ion plating, or plating. The photoelectric conversion element of the present disclosure is manufactured by the above steps.

[0371] (Sealing body forming process) To form the sealed body, any suitable sealing material (adhesive) and substrate (sealing substrate) known in the art are used. Specifically, a sealing material such as a UV-curable resin is applied to a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the support substrate and the sealing substrate are bonded together without any gaps using the sealing material. After that, the photoelectric conversion element is sealed in the gap between the support substrate and the sealing substrate using a method suitable for the selected sealing material, such as UV light irradiation, thereby obtaining a sealed photoelectric conversion element.

[0372] <Photodetector element> As described above, the photoelectric conversion element of the present disclosure, particularly the photodetector element (photosensor), can function by being incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device). [Example]

[0373] Examples are provided below to further explain the present disclosure, but the present disclosure is not limited to the examples described below.

[0374] In the photoelectric conversion element of this example, PCE-10 manufactured by 1-material Co., Ltd., shown in Table 1 below, was used as a p-type semiconductor material (electron donor compound), and the compound shown in Table 2 below was used as an n-type semiconductor material (electron acceptor compound).

[0375] [Table 1]

[0376] [Table 2]

[0377] Compounds N-1, N-2, and RN-1, which are n-type semiconductor materials, were synthesized according to the synthesis examples described below and used.

[0378] <Synthesis of Compound N-1> (Synthesis Example 1: Synthesis of Compound 2) As shown in the following formula, compound 2 was synthesized using compound 1.

[0379] [ka]

[0380] A 100 mL four-neck flask was purged with nitrogen and charged with 60% sodium hydride (3.68 g, 92.06 mmol) and THF (23.3 mL). 2-hexyl-1-decanol (26.6 mL, 92.06 mmol) was added dropwise. After stirring at room temperature for 2 hours, the mixture was heated to 70 °C. Compound 1 (5.43 g, 60.97 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 70 °C and stirred for 2 hours. The reaction solution was cooled to room temperature and quenched with saturated aqueous ammonium chloride. The solids were removed by filtration through Celite while rinsing with heptane. The filtrate was washed three times with water and then concentrated on a rotary evaporator to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (heptane / ethyl acetate = 5 / 1) to obtain 22.86 g of compound 2 (14% yield). The NMR spectrum of compound 2 was analyzed. The results are as follows: 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.54 (1H), 6.10 (1H), 3.98 (2H), 1.76 (1H), 0.80-1.56 (30H)

[0381] (Synthesis Example 2: Synthesis of Compound 3) As shown in the following formula, compound 3 was synthesized using compound 2.

[0382] [ka]

[0383] A 500 ml four-neck flask was purged with nitrogen and charged with compound 2 (4.70 g, 14.43 mmol) and THF (105.7 ml). The flask was cooled to -75 °C in a dry ice / acetone bath. A 1.6 M nBuLi hexane solution (9.53 ml, 15.15 mmol) was added dropwise at -75 °C and stirred for 1.5 hours. N-formylpiperidine (16.01 ml, 14.43 mmol) was then added dropwise and the mixture was warmed to room temperature. After stirring at room temperature for 2 hours, the reaction vessel was placed in an ice bath and quenched with 20% aqueous ammonium chloride solution. Heptane was added, the aqueous layer was removed, and the mixture was washed once with water. The organic layer was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated on a rotary evaporator to obtain 4.42 g of crude product. The crude product was used in the next reaction without purification. The NMR spectrum of compound 3 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.87 (1H) ,6.62 (1H), 4.11 (2H), 1.83 (1H), 0.80-1.56 (30H)

[0384] (Synthesis Example 3: Synthesis of Compound 4) As shown in the following formula, compound 4 was synthesized using compound 3.

[0385] [ka]

[0386] A 100 mL four-neck flask was purged with nitrogen, and compound 3 (5.10 g) and chloroform (53.7 ml) were added and cooled to 2 °C in an ice bath. N-bromosuccinimide (2.96 g, 16.63 mmol) was then added in three portions and stirred for 1 hour. The reaction solution was quenched with a 3% aqueous sodium sulfite solution, and the organic layer was extracted with chloroform and washed with water. The organic layer was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated on a rotary evaporator to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (heptane / ethyl acetate = 20 / 1) to obtain 4.94 g of compound 4. The NMR spectrum of compound 4 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.74 (1H), 4.31 (2H), 1.81 (1H) 0.80- 1.56(30H)

[0387] (Synthesis Example 4: Synthesis of Compound 6) As shown in the following formula, compound 6 was synthesized using compound 5.

[0388] [ka]

[0389] 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 6.

[0390] (Synthesis Example 5: Synthesis of Compound 7) As shown in the following formula, Compound 7 was synthesized using Compound 4 and Compound 6.

[0391] [ka]

[0392] A 100 mL four-neck flask was purged with nitrogen and charged with compound 6 (1.40 g, 2.13 mmol), compound 4 (2.03 g, 4.70 mmol), and THF (28.3 mL). After 30 minutes of nitrogen bubbling, Pd2(dba)3 (0.0979 g, 0.107 mmol), [(tBu)3PH]BF4 (0.062 g, 0.214 mmol), and 3M K3PO4 aqueous solution (2.85 mL) were added and the temperature was raised to 60 °C. After 2 hours of incubation, the reaction solution was cooled to room temperature, diluted with toluene, and washed twice with water. The mixture was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated on a rotary evaporator to obtain a crude product. The resulting crude product was purified by recycled GPC (chloroform) to obtain 0.93 g of compound 7 (39% yield). NMR spectra of compound 7 were analyzed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.79 (2H),4.48 (4H),1.91(6H), 0.50- 1.50(90H)

[0393] (Synthesis Example 6: Synthesis of Compound N-1) As shown in the following formula, Compound N-1 was synthesized using Compound 7 and Compound 8.

[0394] [ka]

[0395] A 50 mL three-neck flask was charged with compound 7 (0.647 g, 0.578 mmol), compound 8 (0.470 g, 1.73 mmol) (synthesized according to the method described in WO 2020 / 109823), magnesium sulfate (0.323 g), paratoluenesulfonic acid monohydrate (0.329 g, 1.73 mmol), toluene (12.9 g), and ethanol (5.8 g). The mixture was then heated in an oil bath at 65 °C for 3 hours. The reaction solution was cooled to room temperature, filtered to remove the magnesium sulfate, and concentrated. The concentrate was dissolved in chloroform (22.6 g) and reprecipitated by adding methanol (72.8 g). The crude product was then filtered to obtain a crude product. The resulting crude product was purified by recycled GPC (chloroform) to obtain 0.366 g (41% yield) of compound N-1 as a black solid. The NMR spectrum of compound N-1 was analyzed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.03(2H).8.98 (2H),8.20(2H), 7.69 (2H), 4.59 (4H), 1.95 (6H), 0.50- 1.50(90H)

[0396] <Synthesis of Compound N-2> Compound 10 was synthesized using compound 9.

[0397] [ka]

[0398] A 300 mL four-neck flask was charged with 3-Methoxythiophene (Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-Hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH·HO (0.833 g, 4.38 mmol), and toluene (100 g). The atmosphere was replaced with nitrogen and the mixture was heated to 110 °C. After stirring for 23 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified using a silica gel column (eluent: hexane = 100 wt%) to obtain 13.4 g of compound 10 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 10 was analyzed. The results are as follows. 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)

[0399] Compound 11 was synthesized using compound 10.

[0400] [ka]

[0401] A 200 mL four-neck flask was charged with compound 10 (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 11. The NMR spectrum of the resulting compound 11 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)

[0402] Compound 12 was synthesized using compound 11.

[0403] [ka]

[0404] Crude compound 11 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (JiangSu GR-Chem Co., Ltd.), and THF (149 mL) were charged into a 500 mL four-neck flask and nitrogen bubbling was performed for 30 minutes. Pd2(dba)3 (0.600 g, 0.655 mmol), P(tBu3)HBF4 (0.399 g, 1.38 mmol), and 3 mol / L K3PO4 aqueous solution (60.6 g) were added in that order, and the temperature was raised to 65 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 3.72 g of compound 12 as a yellow-brown liquid. The NMR spectrum of the obtained compound 4 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)

[0405] Compound 12 was used to synthesize compound 13.

[0406] [ka]

[0407] A 100 mL four-neck flask was charged with compound 12 (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 13 as a yellow-brown liquid. The NMR spectrum of the resulting compound 5 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)

[0408] Compound 15 was synthesized using compound 14.

[0409] [ka]

[0410] 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) and THF (11.2 mL). The flask was purged with nitrogen and then cooled to -73 °C. nBuLi (1.56 mol / L in hexane, 1.75 mL, 2.73 mmol) was added and the internal temperature was maintained at -65 °C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.85 mL, 3.72 mmol) and THF (5.6 mL) were added to the dropping funnel and added dropwise to the reaction mass at an internal temperature of -65 °C. After the addition was complete, the internal temperature was maintained at -65 °C for 1 hour, then the temperature was raised to room temperature and the mixture was stirred for 1 hour. After quenching by pouring in 20% aqueous ammonium chloride solution (5.3 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 1.49 g of crude compound 15.

[0411] Compound 16 was synthesized using compound 13 and compound 15.

[0412] [ka]

[0413] Crude compound 15 (1.49 g), compound 13 (2.05 g, 3.20 mmol), and THF (29.6 g) were charged into a 100 mL four-neck flask and subjected to nitrogen bubbling for 30 minutes. Pd2(dba)3 (0.113 g, 0.123 mmol), P(tBu3)HBF4 (0.0749 g, 0.258 mmol), and 3 mol / L K3PO4 aqueous solution (11.4 g) were added in that order and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated on a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 1.27 g of compound 16 as a red liquid. The NMR spectrum of the obtained compound 16 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.20 (1H), 7.13-7.10 (m, 2H), 6.93-6.91 (m, 1H), 4.10 (2H), 4.05

[0414] Compound 17 was synthesized using compound 16.

[0415] [ka]

[0416] A 100 mL four-neck flask was charged with compound 16 (2.27 g, 2.35 mmol), neopentyl glycol (0.43 g, 4.15 mmol), 10-camphorsulfonic acid (0.05 g, 0.21 mmol), and toluene (50 mL). After purging with nitrogen, the mixture was heated to 80 °C and stirred for 3 h. After cooling to room temperature, the mixture was quenched with a 5% aqueous solution of K3PO4. After washing twice with water, the organic layer was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 2.20 g of compound 17 as a red liquid (89% yield). The NMR spectrum of the resulting compound 17 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ7.07(1H),6.95(2H), 6.89(2H), 5.54(1H), 4.01(4H), 3.75(2H), 3.62(2H), 1.85(6H), 0.55-1.60(80H)

[0417] Compound 17 was used to synthesize compound 18.

[0418] [ka]

[0419] A 100 mL four-neck flask was charged with compound 17 (1.769 g, 1.685 mmol), bis(pinacolato)diboron (0.535 g, 2.106 mmol), 4,4'-di-tert-butyl-2,2'-dipyridyl (0.022 g, 0.0008 mmol), [Ir(OMe)(cod)]2 (0.0027 g, 0.0004 mmol), and cyclohexane (34 mL). After purging with nitrogen, the internal temperature was raised to 80 °C and stirred for 2 h. A separate 100 mL four-neck flask was charged with 8.48 g of water, and the reaction mass, cooled to room temperature, was added dropwise. The aqueous layer was removed by separation, the organic layer was dried over magnesium sulfate, and then filtered through silica gel. The resulting filtrate was concentrated on a rotary evaporator to give 1.98 g of compound 18 (84% yield). The NMR spectrum of the obtained compound 18 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D)δ7.42(1H),6.98(2H), 6.91(1H), 5.54(1H), 4.01(4H), 3.76(2H), 3.64(2H), 1.84(6H), 0.55-1.60(80H)

[0420] Compound 19 was synthesized using compound 18 and compound 4.

[0421] [ka]

[0422] A 100 mL four-neck flask was purged with nitrogen and charged with compound 18 (1.00 g, 0.752 mmol), compound 4 (0.390 g, 0.902 mmol), and THF (22.6 mL). Nitrogen bubbling was performed for 30 minutes. Pd2(dba)3 (0.0344 g, 0.0376 mmol), P(tBu3)HBF4 (0.0229 g, 0.0789 mmol), and 3 mol / L K3PO4 aqueous solution (2.51 mL) 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 reaction mass was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to the full volume using a rotary evaporator. The resulting crude product was purified by recycled GPC (chloroform) to obtain 0.421 g of compound 19 (40% yield). The NMR spectrum of the obtained compound 19 was analyzed, and the results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D)δ9.77(1H), 7.31(1H), 7.03(1H), 6.98(1H), 6.93(1H), 5.56(1H), 4.45(2H), 4.03(4H), 3.77(2H), 3.64(2H), 1.88(7H), 0.55-1.60(110H)

[0423] Compound 20 was synthesized using compound 19.

[0424] [ka]

[0425] A 50 mL four-neck flask was purged with nitrogen and charged with compound 19 (0.323 g, 0.230 mmol), THF (15.1 mL), water (3.78 mL), and trifluoroacetic acid (0.353 mL). The mixture was cooled in an ice bath and stirred for 3 hours. The reaction solution was diluted with heptane, quenched with 5% aqueous disodium hydrogen phosphate, and then washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then completely concentrated on a rotary evaporator to obtain a crude product. The crude product was purified by recycled GPC (chloroform) to obtain 0.386 g of compound 20 (97% yield). The NMR spectrum of the resulting compound 20 was analyzed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D) δ9.78(1H),9.76(1H), 7.48(1H), 7.32(1H), 7.20(1H), 7.12(1H), 4.47(2H), 4.11(2H), 4.06(2H), 1.88(7H), 0.55-1.70(104H)

[0426] Compound 20 was used to synthesize compound N-2.

[0427] [ka]

[0428] A 50 mL three-neck flask was charged with compound 20 (0.363 g, 0.276 mmol), compound 8 (0.202 g, 0.828 mmol), p-TsOH·HO (0.157 g, 0.828 mmol), EtOH (4.1 mL), toluene (8.4 mL), and MgSO (0.182 g). The mixture was then placed in an oil bath heated to 65 °C and allowed to cool to room temperature. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated using an evaporator and repulped with methanol to obtain a crude product. The resulting crude product was purified by recycling GPC to obtain 0.210 g (43% yield) of compound N-2 as a black solid. NMR spectroscopy of the resulting compound N-2 was performed. The results are shown below. 1 H-NMR (300 MHz, CHLOROFORM-D)δ8.99(2H), 8.89(1H), 8.78(1H), 8.14(2H), 7.71(1H), 7.50(2H), 7.32(1H), 4.58(2H), 4.19(4H), 1.99(7H), 0.55-1.70(104H)

[0429] <Synthesis of compound RN-1> (Synthesis Example 7: Synthesis of Compound 21) As shown in the following formula, compound 21 was synthesized using compound 6.

[0430] [ka]

[0431] Crude compound 6 (0.775 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.870 g, 2.72 mmol), and THF (7.0 g) were charged into a 50 mL three-neck flask and nitrogen was bubbled through for 30 minutes. Pd2(dba)3 (0.054 g, 0.06 mmol), P(tBu3)HBF4 (0.034 g, 0.12 mmol), and 3M K3PO4 aq (2.19 g) were added in that order, and the temperature was raised to 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: heptane / ethyl acetate = 100 / 0 to 75 / 25 wt%) to obtain 0.521 g (50% yield) of compound 21 as a reddish-purple viscous liquid. The NMR spectrum of compound 21 was analyzed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.47 (2H), 7.32 (2H), 4.11 (4H), 1.79-1.96 (m, 6H), 1.37-171 (m, 16H), 0.88-1.02(m, 28H), 0.60-0.73(m, 14H)

[0432] (Synthesis Example 8: Synthesis of Compound RN-1) As shown in the following formula, compound RN-1 was synthesized using compound 21.

[0433] [ka]

[0434] A 50 mL four-neck flask was charged with compound 21 (0.521 g, 0.59 mmol), compound 8 (0.434 g, 1.78 mmol), p-TsOH·HO (0.338 g, 1.78 mmol), EtOH (4.7 g), toluene (10.4 g), and MgSO (0.26 g) and kept warm in an oil bath heated to 65 °C. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The MgSO was removed by filtration, and the precipitate was dissolved and washed with chloroform. The mixture was concentrated using an evaporator and repulped with methanol to obtain a crude product. The resulting crude product was purified using a silica gel column (eluent: chloroform = 100 wt%) and then repulped with acetone to obtain 0.432 g (55% yield) of the target product as a blue-green-black solid. NMR spectra of the resulting product were analyzed. The results are as follows: 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.00 (2H), 8.79 (2H), 8.17 (2H), 7.73 (2H), 4.21 (4H), 1.89-2.08 (m, 6H), 1.40-1.73 (m, 16H), 0.95-1.06 (m, 28H), 0.64-0.74 (m, 14H)

[0435] <Measurement of the maximum absorption wavelength of a solution> Compound N-1, compound N-2, and compound RN-1 were each added to orthodichlorobenzene to a concentration of 0.00125% by mass to obtain a solution for UV-Vis spectrum measurement. The maximum absorption wavelength (λmax) was measured using this solution. Details of the measurement method are as described above.

[0436] [Table 3]

[0437] <Measurement of the optical absorption edge wavelength (λth) of thin films> Compounds N-1, N-2, and RN-1 were each added to orthodichlorobenzene to a concentration of 1.0% by mass. The mixture was heated and stirred for 4 hours at 65°C under a nitrogen atmosphere to prepare a solution. The filtrate was used as the coating solution. The coating solution was placed on a glass substrate whose surface had been cleaned with UV-ozone, and a film was formed by spin coating. The spin-coated coating film was placed on a hot plate. It was then dried in air at 70°C for 5 minutes to obtain a thin film for UV-Vis spectrum measurement. The optical absorption edge wavelength (λth) of this thin film was measured using the method described above.

[0438] [Table 4]

[0439] <Evaluation of photoelectric conversion elements> [Preparation of Ink (I-1)] The following components were mixed and stirred at room temperature for 12 hours, and the resulting mixture was filtered to obtain ink (I-1). P-type semiconductor material: polymer compound P-19...0.8% by mass N-type semiconductor material: Compound N-1...0.56% by mass n-type semiconductor material: C60PCBM...0.24 mass% Solvent: Chloroform / 1-chloronaphthalene = 98 wt% / 2 wt% ... remaining amount to make 100% by mass of the entire ink

[0440] 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.

[0441] [Preparation of Ink (I-2)] Ink (I-2) was obtained in the same manner as in the preparation of ink (I-1), except that compound N-1 was changed to compound N-2.

[0442] [Preparation of Ink (II-1)] Ink (II-1) was obtained in the same manner as in the preparation of ink (I-1), except that compound N-1 was changed to compound RN-1.

[0443] [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.

[0444] Next, a solution of 80% ethoxylated polyethyleneimine aqueous solution (Sigma-Aldrich, 37% by mass aqueous solution) (ETL-1) diluted 500 times with water or a zinc oxide dispersion (Avantama, product name N-10) (ETL-2) was applied to the cleaned glass substrate by spin coating to form a coating film, which was then placed on a hot plate and dried in air at 120°C for 10 minutes to form an electron transport layer (hereinafter also referred to as "ETL").

[0445] Next, ink (I-1) was applied onto the electron transport layer by spin coating to form a coating film, which was then dried by heating for 5 minutes on a hot plate heated to 70°C in air (pre-bake step), and then heated for 10 minutes on a hot plate at 100°C in a nitrogen atmosphere (post-bake step) to form an active layer. The thickness of the formed active layer was approximately 400 nm.

[0446] 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.

[0447] 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.

[0448] 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.

[0449] [evaluation] With a reverse bias voltage of 3 V applied to the obtained photoelectric conversion element, a monochromatic light of 1450 nm (photon count: 1 × 10) was measured using a spectral sensitivity measurement device (manufactured by Bunkoukeiki Co., Ltd., product name: CEP-25SC type). 14 ) was irradiated onto the photoelectric conversion element, the generated current value was measured, and a photodiode drive test was performed using a known method. In this test, if photoelectric conversion was confirmed, it was judged as Y, and if photoelectric conversion was not confirmed, it was judged as N.

[0450] [Table 5]

[0451] It has been found that a photoelectric conversion element using the compound of the present disclosure as an n-type semiconductor material is capable of photoelectric conversion up to a longer wavelength (1450 nm) compared to a photoelectric conversion element using a conventional n-type semiconductor material.

[0452] <Energy band gap (Eg) and wavelength λ corresponding to the energy band gap Eg > As a calculation example, the energy band gaps (Eg) of compounds N-1-1 to N-1-4 and N-2 to N-7, which are n-type semiconductor materials in this embodiment, were calculated using a computational science method. Similarly, as a calculation comparison example, the energy band gaps (Eg) of compounds RN-1-1 to RN-1-2, RN3-1 to RN-3-2, RN-4-1 to RN-4-2, and RN-5 to RN-7 were calculated using a computational science method.

[0453] Specifically, using the quantum chemistry calculation program Gaussian 03, the ground state structure was 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 was taken as the value of the ground state energy level. Next, the energy level of the exciton singlet state was 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 exciton singlet state and the energy level of the ground state was taken as the energy level band gap (Eg). The wavelength λ corresponding to the energy band gap Eg was calculated using Equation 1. λ Eg = 1240 / Eg (Equation 1)

[0454] The results are shown in the following Tables 6 to 8. In addition, in the calculation, a propyl group (-CH2-CH2-CH3) was used as an example of a representative alkyl group that can be contained in the compound (structure).

[0455] [Table 6]

[0456] [Table 7]

[0457] [Table 8]

[0458] As described above, it was shown that the compounds of the calculation examples have smaller energy band gaps and longer wavelengths corresponding to the energy band gaps compared to the corresponding compounds of the calculation comparison examples. [Explanation of symbols]

[0459] 10 Photoelectric conversion element 11 Support substrate 12 Anode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Cathode 17 Sealing member

Claims

1. A compound represented by the following formula (1): 【Chemical 1】 (In formula (1), D represents a divalent group containing two or more fused or linked aromatic rings, and containing four or more double bonds in a conjugated structure connecting the bond between D and p1 and the bond between D and p2 in the shortest distance; p1 and p2 represent a divalent group, and at least one of p1 and p2 is a divalent group containing at least one unit represented by the following formula (TZ), and p1 and p2 may be the same or different: Each A independently represents an electron-withdrawing monovalent group. 【Chemistry 2】 In the formula (TZ), * represents a bond to the D side in formula (1), ** represents a bond to the A side in formula (1), X １ represents an electron-donating group.)

2. The compound according to claim 1, wherein p1 or p2 is a divalent group containing at least one unit represented by formula (TZ).

3. The compound according to claim 1, represented by the following formula (2): 【Chemistry 3】 (In formula (2), D and two A are electron donating groups X １ are linked to each other via a thiazole ring substituted with D represents a divalent group containing two or more fused or linked aromatic rings, and having four or more double bonds in a conjugated structure connecting two bonds between D and the two thiazole rings at the shortest distance; Each A independently represents an electron-withdrawing monovalent group.

4. X １ are each independently -R ＴＺ , -OR ＴＺ , -NR ＴＺ ２ , and -SR ＴＺ is an electron-donating group selected from the group consisting of R ＴＺ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic; A compound according to claim 1 or claim 3.

5. The compound according to claim 1 or 3, wherein D is any structure selected from the group consisting of the following formulas (D-1) to (D-4): 【Chemistry 4】 In formula (D-1) and formula (D-2), X is any of the groups represented by the following formulas (X-1) to (X-6): 【Chemistry 5】 In formula (D-3), formula (D-4), and formula (X-1) to formula (X-6), R ｄ are each independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In formula (D-2), Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and which may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and which may be further condensed with a plurality of ring structures.

6. The compound according to claim 1 or claim 3, wherein A is each independently any one of groups represented by the following formula (a-1) to formula (a-5): 【Chemistry 6】 (In the above formulas (a-1) to (a-5), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and heterocyclic ring may be a single ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different. X ４ , X ５ , and X ６ are each independently an oxygen atom, a sulfur atom, an alkylidene group, ═C(—CN) ２ or =C(-CN)-CR ａ represents a group represented by R ａ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aromatic alkyl group having 5 to 30 carbon atoms, an aromatic alkenyl group having 5 to 30 carbon atoms, or an aromatic alkynyl group having 5 to 30 carbon atoms, and the alkyl group, alkenyl group, alkynyl group, aromatic alkyl group, aromatic alkenyl group, and aromatic alkynyl group may have a substituent and may be linear, branched, or cyclic.

7. A composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises the compound according to claim 1 or 3.

8. The composition according to claim 7, wherein the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): 【Chemistry 7】 (In formula (3), Ar ３ and Ar ４ each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulas (Z-1) to (Z-7): 【Chemistry 8】 In formulas (Z-1) to (Z-7), Each R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different, In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

9. An ink comprising the compound according to claim 1 or 3 and a solvent.

10. an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material; A photoelectric conversion element comprising the compound according to claim 1 or 3 as the n-type semiconductor material.

11. The photoelectric conversion element according to claim 10, which is a photodetector element.

12. An optical sensor comprising the photoelectric conversion element according to claim 11.

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