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

Abstract

The present invention addresses the problem of providing: a novel compound; a composition and an ink that contain the compound; a photoelectric conversion element having lower dark current; and a light sensor.　A means for solving this problem is this compound represented by a formula (1). In formula (1), D moieties are each independently a polycyclic aromatic group having two bonding sites; there are four or more double bonds in a conjugated structure that connects these two bonding sites by the shortest distance; L1 and L1' each independently denote an aromatic group having two bonding sites; there are three or fewer double bonds in a conjugated structure that connects these two bonding sites by the shortest distance; L2 is not the same chemical structure as D, and is an aromatic group having two bonding sites; n is 1 or 2; m is 0 or 1; n+m=2; and A1 and A2 are acceptor groups.

Description

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

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

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

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

[0004] Non-Patent Document 1 discloses that it is important to minimize dark current in organic photodetectors (OPDs), which are a type of photoelectric conversion element. Reducing the dark current can improve important performance indices such as the signal-to-noise ratio, linear dynamic range, and specific detectivity of the photoelectric conversion element.

[0005] G. Simone et al., Organic Photodetectors and their Application in Large Area and Flexible Image Sensors: The Role of Dark Current, Adv. Funct. Mater. 2020, 30, 1904205

[0006] Non-fullerene acceptors (NFAs) are known as compounds that can be used in photoelectric conversion elements, but the dark current of photoelectric conversion elements using conventional NFAs is not sufficiently low. The present disclosure has been made in view of the above, and relates to the provision of novel compounds, compositions and inks containing the compounds, photoelectric conversion elements with reduced dark current, and optical sensors.

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

[0008]

[0009] In formula (1), D's are each independently a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds, L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds, L2 does not have the same chemical structure as D and is an aromatic group having two bonds, n is 1 or 2, m is 0 or 1, and n+m=2, and A1 and A2 are acceptor groups. <2> The compound according to <1>, represented by the following formula (2):

[0010]

[0011] In formula (2), D is a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds, L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds, L2 is an aromatic group having two bonds and does not have the same chemical structure as D, and A1 and A2 are acceptor groups. <3> The compound according to <1> or <2>, wherein the polycyclic aromatic group contains a five-membered ring structure, and the two bonds of the polycyclic aromatic group each extend from the five-membered ring structure. <4> The compound according to any one of <1> to <3>, wherein the conjugated structure connecting the two bonds at the shortest distance in L2 contains three or less double bonds. <5> The compound according to any one of <1> to <4>, wherein L1, L1', and L2 each independently contain two or less double bonds in the conjugated structure connecting the two bonds at the shortest distance. <6> The compound according to any one of <1> to <5>, wherein in D, the polycyclic aromatic group has a side chain, the carbon to which the side chain is bonded is an sp3 carbon or an sp2 carbon, and the side chain has an aromatic ring or a branched chain. <7> The compound according to any one of <1> to <6>, wherein L1, L1', and L2 all have different chemical structures, or any two of L1, L1', and L2 have the same chemical structure. <8> The compound according to any one of <1> to <7>, wherein D is a donor group and has a side chain having 6 or more carbon atoms. <9> The compound according to any one of <1> to <8>, wherein D, L1, L1', and L2 all have a sulfur-containing heterocycle. <10> The compound according to any one of <1> to <9>, wherein D is each independently any group represented by the following formula (D-1) to formula (D-7):

[0012]

[0013] In formulas (D-1), (D-2), (D-6) and (D-7), X is any of the groups represented by the following formulas (X-1) to (X-6).

[0014]

[0015] In formulas (D-3) to (D-7) and formulas (X-1) to (X-6), R Ｄ１ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ <11> The compound according to any one of <1> to <10>, wherein L1 and L1′ are each independently any group represented by the following formulae (L1-1) to (L1-9):

[0016]

[0017] In formulas (L1-1) to (L1-9), R Ｌ１each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group. <12> The compound according to any one of <1> to <11>, wherein L2 is each independently any group represented by the following formula (L2-1) to formula (L2-9):

[0018]

[0019] In formulas (L2-1) to (L2-9), R Ｌ２each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group. <13> The compound according to any one of <1> to <12>, in which A1 and A2 are each independently any group represented by the following formulas (a-1) to (a-8):

[0020]

[0021] In formulas (a-1) to (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group. <14> A composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises the compound described in any one of <1> to <13>. <15> The composition according to <14>, 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):

[0022]

[0023] 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):

[0024]

[0025] In formulae (Z-1) to (Z-7), R each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or 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. ５represents a divalent aromatic heterocyclic group. <16> An ink comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the n-type semiconductor material comprises the compound described in any one of <1> to <13>. <17> A photoelectric conversion element comprising an anode, a cathode, and an active layer provided between the anode and the cathode and comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises the compound described in any one of <1> to <13>. <18> The photoelectric conversion element according to <17>, which is a light detection element. <19> An optical sensor comprising the photoelectric conversion element according to <18>. <20> A composition comprising a compound represented by the following formula (1) and a polymer compound comprising at least one structural unit 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):

[0026]

[0027] In formula (1), D's are each independently a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds; L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds; L2 does not have the same chemical structure as D and is an aromatic group having two bonds; n is 1 or 2, m is 0 or 1, and n+m=2; and A1 and A2 are each independently an acceptor group of any of the following formulae (a-5) to (a-8).

[0028]

[0029] 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):

[0030]

[0031] In formulas (Z-1) to (Z-7), R each independently represents an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, or a cycloalkyl group which may have a substituent, and when there are two R in each of formulas (Z-1) to (Z-7), the two R may be the same as or different from each other. ５ represents a divalent aromatic heterocyclic group.

[0032]

[0033] In formulas (a-5) to (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.

[0034] According to the present disclosure, there are provided a novel compound, a composition and ink containing the compound, a photoelectric conversion element with reduced dark current, and an optical sensor.

[0035] FIG. 1 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element.

[0036] 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.

[0037] 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.

[0038] In the present disclosure, when a numerical range is indicated using "to", the numerical values ​​before and after "to" are included as the lower and upper limits, respectively. In the present disclosure, when a numerical range is described in stages, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another staged numerical range. Furthermore, in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, when multiple substances corresponding to each component are present in the composition, the content of each component refers to 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", it does not exclude the combination of multiple elements unless a technical contradiction occurs, unless otherwise specified. In the present disclosure, when an element is described in the singular, it does not exclude the presence of multiple elements unless a technical contradiction occurs, unless otherwise specified. In the present disclosure, multiple exemplary embodiments described separately may be combined with each other to form a new embodiment, unless mutually contradictory.

[0039] The following describes commonly used terms in this disclosure. In the description of this disclosure, the following descriptions apply unless otherwise specified.

[0040] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0041] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0042] The term "polymer compound" refers to a compound having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1×10 ３ 1x10 or more ８ The total amount of structural units contained in the polymer compound is 100 mol %.

[0043] 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.

[0044] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0045] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0046] The embodiment in which "may have a substituent" includes both a case in which all hydrogen atoms constituting the compound or group are unsubstituted, and a case in which one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0047] 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, when referring to the number of carbon atoms, the number of carbon atoms does not usually include the number of carbon atoms of the substituent.

[0048] In this specification, unless otherwise specified, an "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 of substituents, 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 of substituents, is usually preferably 3 to 50, more preferably 3 to 30, and even more preferably 4 to 20.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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 of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0053] 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.

[0054] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0055] 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 which 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.

[0056] The term "aryl group" refers to a monovalent aromatic carbocyclic group, which is an 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.

[0057] 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 has been substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0058] The "alkyloxy group" (alkoxy group) may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkyloxy group, not including the number of carbon atoms of 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 of the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] The number of carbon atoms in the "aryloxy group" is usually preferably 6 to 60, more preferably 6 to 48, not including the number of carbon atoms of the substituents.

[0063] 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 has been substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0064] 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 of substituents, 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 of substituents, is usually preferably 3 to 40, more preferably 4 to 10.

[0065] 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.

[0066] 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 of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0067] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0068] The number of carbon atoms in the "arylthio group" is usually preferably 6 to 60, more preferably 6 to 48, not including the number of carbon atoms of the substituents.

[0069] 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.

[0070] 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.

[0071] The heterocyclic group may further have a substituent. The number of carbon atoms of the heterocyclic group is usually preferably 2 to 30, more preferably 2 to 6, not including the number of carbon atoms of the substituent.

[0072] Examples of the substituent 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."

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] The number of carbon atoms in the monovalent heterocyclic group is usually preferably 2 to 60, more preferably 4 to 20, not including the number of carbon atoms in the substituent.

[0078] 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.

[0079] 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, with an alkyl group, an aryl group, or a monovalent heterocyclic group being preferred. The number of carbon atoms in the substituted amino group is usually preferably 2 to 30.

[0080] 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.

[0081] The "acyl group" may have a substituent. The number of carbon atoms in the acyl group, not including the number of carbon atoms of 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.

[0082] 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.

[0083] The imine residue generally preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the following structural formula: In the following structural formula, Me represents a methyl group.

[0084]

[0085] 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.

[0086] The term "acid imide group" refers to the atomic group remaining after removing one hydrogen atom bonded to the nitrogen atom from an acid imide. The number of carbon atoms in an acid imide group is usually preferably 4 to 20. Specific examples of acid imide groups include groups represented by the following structural formula: In the structural formula, Me represents a methyl group.

[0087]

[0088] The term "substituted carbonyl group" refers to a group represented by -(C=O)-R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0089] The "substituted oxycarbonyl group" is a group represented by -(C=O)-O-R 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.

[0090] The "substituted sulfonyl group" is a group represented by -SO ２ -R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0091] The term "substituted oxysulfonyl group" refers to a group selected from the group consisting of -(SO ２ )-O-R Ｘ or -O-(SO ２ )-R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0092] The number of carbon atoms of the substituted oxycarbonyl group is usually preferably 2 to 60, more preferably 2 to 48, not including the number of carbon atoms of the substituent.

[0093] 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.

[0094] 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 of substituents, 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 of substituents, is usually preferably 3 to 30, more preferably 4 to 20.

[0095] The alkenyl group may have a substituent. Specific examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 7-octenyl, and groups in which hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, or fluorine atoms.

[0096] 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 of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0097] 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.

[0098] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0099] The "alkynyl group" may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkynyl group, not including the number of carbon atoms of substituents, 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 of substituents, is usually preferably 4 to 30, more preferably 4 to 20.

[0100] 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 has been substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0101] 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.

[0102] 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.

[0103] Examples of the substituted cycloalkynyl group include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0104] 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.

[0105] The symbol "*" that may be attached 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 "*" and two dotted lines, there is no particular limitation as to which of the two units to which the bond is attached.

[0106] "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.

[0107] The ink may be a solution or a dispersion such as an emulsion or suspension.

[0108] 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.

[0109] "External quantum efficiency" is also called EQE (External Quantum Efficiency), and refers to a value expressed as a 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.

[0110] <Compound> The compound of the present disclosure is represented by the following formula (1).

[0111]

[0112] In formula (1), D's are each independently a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds; L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds; L2 does not have the same chemical structure as D and is an aromatic group having two bonds; n is 1 or 2, m is 0 or 1, and n+m=2; and A1 and A2 are acceptor groups.

[0113] The compound of the present disclosure is a novel compound that reduces dark current when used in a photoelectric conversion element. The action of the compound of the present disclosure is not clear, but is presumed to be as follows.

[0114] In the compound of the present disclosure, represented by formula (1), the groups represented by L1 and L1′, and (L2) ｍ Each of the groups represented by (D) is a linker. ｎ The group represented by is a core, and the group represented by A1 and the group represented by A2 are each an acceptor. In formula (1) which is the compound of the present disclosure, A1, L1, L1', D, L2, and A2 each represent one structural unit, and the structural unit is referred to as a unit. That is, as represented by formula (1), the compound of the present disclosure is a compound consisting of a total of (4 + n + m) units, namely, A1, L1, L1', n Ds, m L2s, and A2s. Acceptor A1 and (D) ｎ The linker between the acceptor A2 and (D) consists of two units (L1 and L1'). ｎ The linker between the two is m units ((L2) ｍ In a photoelectric conversion element using the compound of the present disclosure, molecules of the compound of the present disclosure are in an associated state via some of the units.

[0115] The causes of dark current in a photoelectric conversion element include current derived from impurity potential in the injection current or current derived from band-to-band transition, and current due to the spread of the density of states (DOS). In particular, when the DOS spreads, electrons become more likely to flow, increasing the value of the dark current. Therefore, in order to reduce the dark current, it is necessary to narrow the spread of the DOS.

[0116] The compound of the present disclosure has an appropriately controlled aggregation state, narrows the spread of DOS, and can reduce dark current in a photoelectric conversion element. Note that the present disclosure is not limited to the above-mentioned assumed mechanism.

[0117] <D; Core> [Polycyclic aromatic group] In formula (1), D's are each independently a polycyclic aromatic group having two bonds (i.e., a divalent polycyclic aromatic group). Note that D's do not have the same chemical structure as L1, L1', and L2 described below, but have different chemical structures.

[0118] The polycyclic aromatic group in D may be either a polycyclic aromatic heterocyclic group or a polycyclic aromatic carbocyclic group, and from the viewpoint of easily absorbing long wavelength light, a polycyclic aromatic heterocyclic group is preferred.The heteroatom in the polycyclic aromatic heterocyclic group is preferably at least one selected from the group consisting of sulfur atom, silicon atom, selenium atom, nitrogen atom and oxygen atom, more preferably at least one selected from the group consisting of sulfur atom, silicon atom, nitrogen atom and oxygen atom, and even more preferably sulfur atom.That is, the polycyclic aromatic group in D preferably has a sulfur-containing heterocycle, more preferably a sulfur-containing heterocyclic group.

[0119] In the polycyclic aromatic group having two bonds in D, the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is preferably 4 to 12, more preferably 4 to 8, even more preferably 4 to 6, still more preferably 4 or 5, and still more preferably 4.

[0120] In view of the ease with which the compound absorbs light of a long wavelength, D in the formula (1) is preferably a donor group (also referred to as a group with donating properties).

[0121] In order to improve the planarity of the compound, it is preferable that the polycyclic aromatic group in D contains a five-membered ring structure and that the two bonds of the polycyclic aromatic group extend from the five-membered ring structure. The polycyclic aromatic group in D preferably contains two or more five-membered ring structures, and more preferably consists of only five-membered ring structures.

[0122] [Side Chain] In the formula (1), it is preferable that the polycyclic aromatic group has a side chain in D. In the present disclosure, the side chain refers to a group that substitutes a hydrogen atom bonded to an atom constituting the main skeleton (such as a single ring or a fused ring). In D, the side chain is preferably a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0123] In D, the side chain preferably has an aromatic ring or a branched chain, and more preferably has a branched chain.

[0124] In D, the polycyclic aromatic group may have a plurality of side chains, and when it has a plurality of side chains, the plurality of side chains may be the same or different from one another.

[0125] 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, more preferably an alkyl group or an aryl group, which may have a substituent, and even more preferably an alkyl group.

[0126] 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.

[0127] The atom in D to which the side chain is bonded is preferably sp3 carbon, sp3 silicon, sp2 carbon, or sp2 silicon, more preferably sp3 carbon or sp2 carbon, and even more preferably sp3 carbon from the viewpoint of reducing dark current. This is because, when a side chain is bonded to an sp3 carbon, the side chain protrudes perpendicularly to the π plane of the ring structure of the polycyclic aromatic group containing an sp3 carbon in the main skeleton, and the association pattern between molecules of the compound of the present disclosure is limited.

[0128] [Chemical Structure of D] In view of the ease with which the compound absorbs light of a long wavelength, D in the formula (1) is preferably each independently any of the groups represented by the following formulas (D-1) to (D-7), and more preferably a group represented by the following formula (D-1), (D-2) or (D-6). In the following formulas (D-1) to (D-7), the symbol "*" indicates a bond to L1' or (L2) when n in formula (1) is 1. ｍ The symbol "*" indicates a bond to L1' or a bond to D, or a bond to D or (L2) when n in formula (1) is 2. ｍ There is no particular limitation as to which bonds the two symbols "*" in the chemical formula represent.

[0129]

[0130] In formulas (D-1), (D-2), (D-6) and (D-7), X is any of the groups represented by the following formulas (X-1) to (X-6).

[0131]

[0132] In formulas (X-1) to (X-6), R Ｄ１ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ Either one of them may not be present.

[0133] Since the polycyclic aromatic group in D preferably has a side chain, the plurality of R Ｄ１ At least one of these is preferably not a hydrogen atom.

[0134] In each of formulas (X-1) to (X-6), RＤ１ If there are two R Ｄ１ may be the same or different. 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 Ｄ１ 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.

[0135] In formula (D-2), formula (D-5) and formula (D-7), Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ Either one of them may not be present.

[0136] Ar １ and Ar ２ The aromatic heterocycle that can constitute the above ring includes not only a single ring and a fused ring in which the heterocycle itself exhibits aromaticity, but also a ring in which an aromatic ring is fused to a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0137] 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.

[0138] Ar １ and Ar ２Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0139] 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.

[0140] The planarity of the compound increases, so Ar １ and Ar ２ each preferably includes a five-membered ring structure, and the two bonds in D each preferably extend from the five-membered ring structure.

[0141] In formulas (D-3) to (D-7), R Ｄ１ The definition and preferred embodiments of R in the above formulas (X-1) to (X-6) are as follows: Ｄ１ is the same as:

[0142] (Examples of D) Examples of formula (D-1) include groups represented by the following formulas (d-1-1) to (d-1-6). Examples of formula (D-2) include groups represented by the following formulas (d-2-1) to (d-2-23). ​​Examples of formula (D-3) include groups represented by the following formulas (d-3-1) to (d-3-6). Examples of formula (D-4) include groups represented by the following formulas (d-4-1) to (d-4-4). Examples of formula (D-5) include groups represented by the following formulas (d-5-1) to (d-5-10). Examples of formula (D-6) include groups represented by the following formulas (d-6-1) to (d-6-2). Examples of formula (D-7) include groups represented by the following formulas (d-7-1) to (d-7-9).

[0143] In addition, in formulas (d-1-1) to (d-1-6), formulas (d-2-1) to (d-2-23), formulas (d-3-1) to (d-3-6), formulas (d-4-1) to (d-4-4), formulas (d-5-1) to (d-5-10), formulas (d-6-1) to (d-6-2), and formulas (d-7-1) to (d-7-9), R Ｄ１ The definitions of each independently are the same as those of R Ｄ１ In the following formulas (d-2-1) to (d-2-23), (d-5-1) to (d-5-10), and (d-7-1) to (d-7-9), U each independently represents CR Ｄ１ ２ , S, SiR Ｄ１ ２ , Se, NR Ｄ１ or O. U is preferably S. In the following formulas (d-1-1) to (d-1-6), (d-2-1) to (d-2-23), (d-3-1) to (d-3-6), (d-4-1) to (d-4-4), (d-5-1) to (d-5-10), (d-6-1) to (d-6-2), and (d-7-1) to (d-7-9), the symbol "*" indicates a bond to L1' or (L2) when n in formula (1) is 1. ｍ The symbol "*" indicates a bond to L1' or a bond to D, or a bond to D or (L2) when n in formula (1) is 2. ｍThere is no particular limitation as to which bonds the two symbols "*" in the chemical formula represent.

[0144] From the viewpoint that the compound easily absorbs light of a long wavelength, D is preferably a group represented by formula (d-1-1), formula (d-1-3) to formula (d-1-6), formula (d-2-3) to formula (d-2-8), formula (d-2-13) to formula (d-2-18), formula (d-3-5) to formula (d-3-6), formula (d-4-1) to formula (d-4-4), formula (d-5-1), formula (d-5-3), formula (d-6-1), formula (d-6-2), or formula (d-7-2) to formula (d-7-5), It is more preferably a group represented by formula (d-1-1), formula (d-1-3) to formula (d-1-6), formula (d-2-3), formula (d-2-5), formula (d-2-8), formula (d-2-13), formula (d-2-15), formula (d-2-18), formula (d-4-1) to formula (d-4-3), formula (d-6-1) or formula (d-6-2), and even more preferably a group represented by formula (d-1-1), formula (d-1-4) to formula (d-1-6), formula (d-2-3), formula (d-2-13) or formula (d-6-1).

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] (Specific Examples of D) Specific examples of D include groups represented by the following formulae: In each formula, the symbol "*" indicates a bond to L1' when n in formula (1) is 1 or a bond to (L2) ｍThe symbol "*" indicates a bond to L1' or a bond to D, or a bond to D or (L2) when n in formula (1) is 2. ｍ There is no particular limitation as to which bonds the two symbols "*" in the chemical formula represent.

[0155]

[0156]

[0157]

[0158]

[0159]

[0160] [(D) ｎ ] In formula (1), (D) ｎ In the formula, n is 1 or 2. From the viewpoint of compound synthesis, n is preferably 1. When n is 2, the two Ds may be the same or different.

[0161] [(D) ｎ Example of (D) ｎ Examples of the groups include groups represented by the following formulae (dn-1-1) to (dn-1-9) and (dn-2-1) to (dn-2-4).

[0162] In the following formulas (dn-1-1) to (dn-1-9) and (dn-2-1) to (dn-2-4), R Ｄ１ The definitions of each independently are the same as those of R Ｄ１ In the following formulas (dn-1-1) to (dn-1-9) and (dn-2-1) to (dn-2-4), the symbol "*" indicates a bond to L1' in formula (1) or a bond to (L2) ｍ This shows the bond between .

[0163] From the viewpoint of compound synthesis, (D) ｎ is preferably a group represented by formula (dn-1-1), formula (dn-1-3), or formula (dn-1-5).

[0164]

[0165]

[0166] <L1 and L1'; A1 and (D) ｎ In formula (1), L1 and L1' are each independently an aromatic group having two bonds (i.e., a divalent aromatic group). Note that L1 and L1' do not have the same chemical structure as D, but have different chemical structures.

[0167] The aromatic group in L1 or L1' preferably has a monocyclic or fused ring main skeleton. The aromatic group in L1 or L1' may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and from the viewpoint of easily absorbing long-wavelength light, an aromatic heterocyclic group is preferred. 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 nitrogen atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the aromatic group in L1 or L1' preferably has a sulfur-containing heterocycle, more preferably a sulfur-containing heterocyclic group. It is more preferable that L1 and L1' are sulfur-containing heterocyclic groups.

[0168] In the aromatic groups L1 and L1' having two bonds, the number of double bonds contained in the conjugated structure connecting the two bonds over the shortest distance is each independently 3 or less. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of double bonds contained in the conjugated structure connecting the two bonds over the shortest distance is preferably 1 to 3, more preferably 2 or less, even more preferably 1 or 2, and even more preferably 2.

[0169] In the formula (1), it is preferable that L1, L1', and L2, which will be described later, all have different chemical structures, or any two of L1, L1', and L2, which will be described later, have the same chemical structure.

[0170] L1, L1' and L2 described below are preferably divalent aromatic heterocyclic groups containing a thiophene ring, which may have a substituent and may have a plurality of condensed ring structures.

[0171] Specifically, L1, L1', and L2 (described later) refer to 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.

[0172] The number of carbon atoms in the divalent aromatic carbocyclic group represented by L1, L1', and L2 described below, not including the number of carbon atoms of the substituents, is usually preferably 6 to 60, more preferably 6 to 20. The number of carbon atoms in the aromatic carbocyclic group including the substituents is usually preferably 6 to 100.

[0173] Examples of the divalent aromatic carbocyclic group represented by L1, L1′, and L2 described below include divalent aromatic carbocyclic groups represented by the following formula: The divalent aromatic carbocyclic group represented by the following formula may further have a substituent.

[0174]

[0175] The divalent aromatic heterocyclic groups represented by L1, L1' and L2 described below usually preferably have 2 to 60 carbon atoms, more preferably 4 to 60 carbon atoms, and even more preferably 4 to 20 carbon atoms.

[0176] Examples of the substituent that the divalent aromatic heterocyclic group represented by L1, L1′, and L2 described later 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.

[0177] Specific examples of the divalent aromatic heterocyclic group represented by L1, L1′, and L2 described later include divalent aromatic heterocyclic groups represented by the following formulas: These groups may further have a substituent.

[0178]

[0179]

[0180]

[0181] The divalent aromatic heterocyclic groups represented by L1, L1′, and L2 described below are preferably divalent aromatic heterocyclic groups represented by the following formula: These groups may further have a substituent.

[0182]

[0183] [Side Chain] The aromatic group in L1 or L1' may have a side chain. In L1 and L1′, the side chains are preferably each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0184] The aromatic group in L1 or L1' may have a plurality of side chains, and when it has a plurality of side chains, the plurality of side chains may be the same or different from one another.

[0185] When a plurality of side chains of the aromatic group in L1 or L1′ are present, each independently is preferably an alkyl group, cycloalkyl group, aryl group, alkyloxy group, aryloxy group, amide group, or substituted oxycarbonyl group, which may have a substituent, more preferably an alkyloxy group, which may have a substituent, and even more preferably an alkyloxy group.

[0186] [Chemical Structure of L1] From the viewpoint of easily reducing the dark current of a photoelectric conversion element using the compound of the present disclosure, in the formula (1), L1 is preferably any of the groups represented by the following formulas (L1-1) to (L1-9), more preferably any of the groups represented by the following formulas (L1-1) to (L1-7), even more preferably any of the groups represented by the following formulas (L1-1) to (L1-4), and even more preferably any of the groups represented by the following formulas (L1-1), (L1-2), or (L1-4). In each formula, the dotted line indicates a bond to A1 in formula (1) or a bond to L1'. There is no particular limitation on whether the dotted line in the chemical formula indicates a bond to A1 or L1'. That is, from the viewpoint that the dark current of a photoelectric conversion element using the compound of the present disclosure is likely to be reduced, and from the viewpoint that the compound is likely to absorb light with a long wavelength, L1 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0187]

[0188] In formulas (L1-1) to (L1-9), R Ｌ１each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0189] In formulas (L1-1) to (L1-9), R Ｌ１ are each independently preferably an alkyl group, cycloalkyl group, aryl group, alkyloxy group, cycloalkyloxy group, aryloxy group, alkylthio 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, which may have a substituent; and even more preferably an alkyl group, alkyloxy group, or substituted oxycarbonyl group.

[0190] (Specific Examples of L1) Specific examples of L1 include groups represented by the following formulae: In each formula, the dotted line indicates a bond to A1 or a bond to L1' in formula (1).

[0191]

[0192]

[0193]

[0194]

[0195] [Chemical Structure of L1'] The explanation of the chemical structure of L1' and specific examples of L1', including definitions, examples, and preferred embodiments, is the same as the explanation of [Chemical Structure of L1] and (Specific Examples of L1) above. In each formula, * and dotted lines indicate bonds to L1 in formula (1) or (D) ｎ In formula (1), the chemical structures of L1 and L1' may be the same or different.

[0196] [Chemical Structure of L1-L1'] The following chemical structures are preferred as the structure of L1-L1'. In each formula, * or dotted line indicates a bond to A1 in formula (1) or (D) ｎ This shows the bond between .

[0197]

[0198] <(L2) ｍ ;A2 and (D) ｎ [Aromatic Group] In formula (1), L2 is an aromatic group having two bonds (i.e., a divalent aromatic group). Note that L2 does not have the same chemical structure as D, but has a different chemical structure.

[0199] The aromatic group of L2 preferably has a monocyclic or fused ring main skeleton. The aromatic group in L2 may be either an aromatic heterocyclic group or an aromatic carbocyclic 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 nitrogen atom, a silicon atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the aromatic group in L2 preferably has a sulfur-containing heterocycle, and more preferably is a sulfur-containing heterocyclic group. It is even more preferable that L2 is a sulfur-containing heterocyclic group.

[0200] In L2, in the aromatic group having two bonds, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is preferably 3 or less. From the viewpoint of reducing dark current in a photoelectric conversion element, the number of double bonds contained in the conjugated structure connecting the two bonds at the shortest distance is more preferably 1 to 3, even more preferably 2 or less, still more preferably 1 or 2, and even more preferably 2.

[0201] As described above, in the formula (1), it is preferable that L1, L1', and L2 all have different chemical structures, or any two of L1, L1', and L2 have the same chemical structure.

[0202] [Side Chain] The aromatic group in L2 may have a side chain. In L2, the side chains are preferably each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0203] The aromatic group in L2 may have a plurality of side chains, and when it has a plurality of side chains, the plurality of side chains may be the same or different from one another.

[0204] When a plurality of side chains of the aromatic group in L2 are present, each side chain is 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, which may have a substituent; and even more preferably an alkyl group, alkyloxy group, or substituted oxycarbonyl group.

[0205] [Chemical Structure of L2] From the viewpoint of easily reducing the dark current of a photoelectric conversion element using the compound of the present disclosure, in the formula (1), L2 is preferably each independently any of the groups represented by the following formulas (L2-1) to (L2-9), more preferably any of the groups represented by the following formulas (L2-1) to (L2-8), and even more preferably any of the groups represented by the following formulas (L2-1), (L2-2), (L2-4) or (L2-7). In each formula, the dotted line represents (D) in formula (1). ｎ or a bond to A2. That is, from the viewpoint that the dark current of a photoelectric conversion element using the compound of the present disclosure is likely to be reduced and that the compound is likely to absorb light with a long wavelength, L2 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0206]

[0207] In formulas (L2-1) to (L2-9), R Ｌ２each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0208] In formulas (L2-1) to (L2-9), R Ｌ２ 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, which may have a substituent; and even more preferably an alkyl group, alkyloxy group, or substituted oxycarbonyl group.

[0209] (Specific examples of L2) Specific examples of L2 are the same as those of L1 above. In each formula, the dotted line represents (D) in formula (1). ｎ This indicates a bond to A1 or a bond to A2.

[0210] [(L2) ｍ] In formula (1), (L2) ｍ In the formula, m is 0 or 1. From the viewpoint of synthesis, m is preferably 1. When m is 0, the formula (D) ｎ and A2 are directly bonded, that is, (L2) ｍ When m is 1, (L2) ｍ The description of is the same as the description of L2 above, including definitions, examples, and preferred embodiments.

[0211] [n and m] As described above, in formula (1), n+m=2. That is, n and m may be any combination of n=1 and m=1, or n=2 and m=0.

[0212] [Examples of Combinations of D and L2] When n and m are n=1 and m=1, examples of combinations of D and L2 include groups represented by the following formulae (dn-3-1) to (dn-3-12), (dn-4-1) to (dn-4-12), (dn-5-1) to (dn-5-12), and (dn-6-1) to (dn-6-12).

[0213] In the following formulas (dn-3-1) to (dn-3-12), (dn-4-1) to (dn-4-12), (dn-5-1) to (dn-5-12), and (dn-6-1) to (dn-6-12), R Ｄ１ The definitions of each independently are the same as those of R Ｄ１ In the following formulas (dn-3-1) to (dn-3-12), (dn-4-1) to (dn-4-12), (dn-5-1) to (dn-5-12), and (dn-6-1) to (dn-6-12), the symbol "*" indicates a bond to L1' or a bond to A2 in formula (1).

[0214] From the viewpoint of compound synthesis, the combination of D and L2 is a group represented by formula (dn-3-1) to formula (dn-3-12), formula (dn-4-1) to formula (dn-4-12), formula (dn-5-1) to formula (dn-5-12), or formula (dn-6-1) to formula (dn-6-12). and is preferably a group represented by formula (dn-3-1), formula (dn-3-4) to formula (dn-3-8), formula (dn-4-1), formula (dn-4-4) to formula (dn-4-8), formula (dn-5-1), formula (dn-5-4) to formula (dn-5-8), or formula (dn-6-1) to formula (dn-6-12), more preferably a group represented by formula (dn-3-1), formula (dn-3-4), formula (dn-4-1), formula (dn-4-4), formula (dn-5-1), or formula (dn-5-4).

[0215]

[0216]

[0217]

[0218]

[0219] <A1 and A2: Acceptor> In the formula (1), A1 and A2 are acceptor groups. In the formula (1), A1 and A2 are preferably each independently a group represented by the following formula (A-1). In each formula, the dotted line represents a bond to L1 in formula (1) or (L2) ｍ This shows the bond between .

[0220]

[0221] In formula (A-1), Ar represents a carbocycle which may have a substituent, or a heterocycle which may have a substituent, and the carbocycle and the heterocycle are each independently a monocycle or a fused ring, and when the carbocycle or the heterocycle has a plurality of substituents, the plurality of substituents may be the same or different.

[0222] The carbocyclic ring may be an aromatic carbocyclic ring. Specific examples of the aromatic carbocyclic ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. Benzene rings and naphthalene rings are preferred, benzene rings and naphthalene rings are more preferred, and benzene rings are even more preferred. These rings may have a substituent.

[0223] The heterocycle may be an aromatic heterocycle. Specific examples of aromatic heterocycles include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0224] [Chemical Structure of A1 and A2] In formula (1), A1 and A2 are preferably each independently any of the groups represented by the following formulae (a-1) to (a-8). In each formula, the symbol "*" indicates a bond to L1 in formula (1) or a bond to (L2). ｍ The chemical structures of A1 and A2 may be the same or different from each other. From the viewpoint of ease of synthesis of the compound, it is preferable that the chemical structures of A1 and A2 are the same.

[0225]

[0226] In formulas (a-1) to (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group. Ａ１are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, or a cyano group, more preferably a cyano group. From the viewpoint that the compound easily absorbs light of a long wavelength, A1 and A2 are each independently preferably any of the groups represented by formula (a-1) or formula (a-3) to formula (a-5), more preferably any of the groups represented by formula (a-1), formula (a-3), or formula (a-5), and even more preferably any of the groups represented by formula (a-1) or formula (a-5).

[0227] (Specific Examples of A1 and A2) Specific examples of A1 and A2 include groups represented by the following formulae: In each formula, the symbol "*" indicates a bond to L1 in formula (1) or (L2) ｍ This shows the bond between .

[0228]

[0229]

[0230] <Compound> The compound of the present disclosure is preferably represented by the following formula (2).

[0231]

[0232] In formula (2), D is a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds; L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds; L2 does not have the same chemical structure as D and is an aromatic group having two bonds; and A1 and A2 are acceptor groups.

[0233] In formula (2), the explanations of D, L1, L1', L2, A1, and A2 are the same as the explanations of D, L1, L1', L2, A1, and A2 in formula (1), including definitions, examples, preferred embodiments, etc.

[0234] In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the compounds of the present disclosure, in formula (1) and formula (2), D is any group represented by formula (D-1) to formula (D-7), L1, L1', and L2 each independently have a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure, A1 and A2 each independently are a group represented by formula (A-1), L1, L1', and L2 are not the same chemical structure as D but are different chemical structures, and in formula (2), it is preferable that n=m=1.

[0235] In the compounds of the present disclosure, in formula (1) and formula (2), D is any group represented by formula (d-1-1) to formula (d-1-6), formula (d-2-3), or formula (d-2-8), L1 and L1' are each independently any group represented by formula (L1-1) to formula (L1-9), L2 is any group represented by formula (L2-1) to formula (L2-9), A1 and A2 are each independently any group represented by formula (a-1) to formula (a-8), L1, L1', and L2 are not the same chemical structure as D but have different chemical structures, L1, L1', and L2 are all different chemical structures from one another, or any two of L1, L1', and L2 have the same chemical structure, and it is more preferable that n=m=1 in formula (2).

[0236] <Specific Examples of Compounds of the Present Disclosure> Specific examples of suitable compounds of the present disclosure include compounds represented by the following formula: In the compounds, tol represents a toluene group.

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] <Composition> The composition of the present disclosure contains a p-type semiconductor material and an n-type semiconductor material, and preferably contains the compound of the present disclosure as the n-type semiconductor material.

[0245] The composition of the present disclosure may contain components other than a p-type semiconductor material and an n-type semiconductor material. Furthermore, 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. The other compounds that may be contained as the n-type semiconductor material may be low molecular weight compounds or high molecular weight compounds.

[0246] <n-Type Semiconductor Material> Examples of low molecular weight compounds that can be included as n-type semiconductor materials include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and phenanthrene derivatives such as bathocuproine.

[0247] Examples of polymer compounds that can be included as n-type semiconductor materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof.

[0248] The other compound may also be a fullerene derivative.

[0249] Here, the fullerene derivative is a fullerene (C ６０ Fullerene, C ７０ Fullerene, C ７６ Fullerene, C ７８ Fullerene and C８４ 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."

[0250] 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 object of the present disclosure.

[0251] C that can be included as an n-type semiconductor material ６０ Specific examples of fullerene derivatives include the following compounds.

[0252]

[0253] Above C ６０In the formula of the fullerene derivative, R represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amido group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group. When there are multiple R's, the multiple R's may be the same or different.

[0254] C ７０ Examples of fullerene derivatives include the following compounds:

[0255]

[0256] <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.

[0257] Here, the weight average molecular weight in terms of polystyrene refers to a weight average molecular weight calculated using a polystyrene standard sample by gel permeation chromatography (GPC).

[0258] The weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in a solvent.

[0259] The p-type semiconductor material is preferably a π-conjugated polymer compound (also referred to as a DA-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). Whether one is a donor structural unit or an acceptor structural unit can be determined relatively from the energy levels of the HOMO or LUMO.

[0260] Here, a donor building block is a building block that has an excess of π electrons, and an acceptor building block is a building block that has a π electron deficiency.

[0261] In the present disclosure, structural units that can constitute a p-type semiconductor material include structural units in which a donor structural unit and an acceptor structural unit are directly bonded, as well as structural units in which a donor structural unit and an acceptor structural unit are bonded via any suitable spacer (group or structural unit).

[0262] Examples of p-type semiconductor materials that are polymer compounds include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, and polyfluorene and derivatives thereof.

[0263] The p-type semiconductor material is preferably 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). The structural unit represented by the following formula (3) is usually preferably a donor structural unit. The structural unit represented by the following formula (4) is usually preferably an acceptor structural unit.

[0264]

[0265] -Formula (3)- In formula (3), Ar ３and 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):

[0266]

[0267] In formulas (Z-1) to (Z-7), R is independently defined as C ６０ The definition of R is the same as that of the fullerene derivative formula. In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different.

[0268] 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.

[0269] Ar ３ and Ar ４ 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.

[0270] 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.

[0271] 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.

[0272] The constitutional unit represented by formula (3) is preferably a constitutional unit represented by the following formula (3-1), (3-2) or (3-3).

[0273]

[0274] In formulas (3-1), (3-2) and (3-3), Ar ３ , Ar ４ and R are defined as Ar in formula (3). ３ , Ar ４ Definition of C ６０ The definition of R in the formula of the fullerene derivative is as follows.

[0275] Specific examples of suitable structural units represented by formula (3) include structural units represented by the following formulas:

[0276]

[0277] In the above formula, R is defined as C ６０ This is the same as the definition of R in the formula of the fullerene derivative. When there are two R, the two R may be the same or different.

[0278] More specific examples of preferred structural units represented by formula (3) include structural units represented by the following formulas:

[0279]

[0280]

[0281] -Formula (4)- In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

[0282] Ar ５ The divalent aromatic heterocyclic group represented by the 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.

[0283] Ar ５ The divalent aromatic heterocyclic group represented by the following formula (1) may have a substituent. ５ Examples of the substituent that the divalent aromatic heterocyclic group represented by the formula (I) may have include a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amide group, an optionally substituted acid imide group, an optionally substituted substituted oxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a cyano group, and a nitro group.

[0284] As the constitutional unit represented by formula (4), constitutional units represented by the following formulae (4-1) to (4-10) are preferred.

[0285]

[0286] In formulas (4-1) to (4-10), R is C ６０ The definition of R in the formula of the fullerene derivative is as follows. ３ and X ４ each independently represents an oxygen atom or a sulfur atom. １ and Z ２ each independently represents a group represented by ═C(R)— or a nitrogen atom. When there are two R, the two R may be the same or different.

[0287] X in formula (4-1) to formula (4-10) ３ and X ４are preferably sulfur atoms from the viewpoint of availability of raw material compounds.

[0288] As described above, the structural units represented by formulas (4-1) to (4-10) can generally function as acceptor structural units. However, without being limited thereto, the structural units represented by formulas (4-4), (4-5), and (4-7) in particular can also function as donor structural units.

[0289] 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.

[0290] Ar ５ Specific examples of the divalent aromatic heterocyclic group represented by the formula (101) include groups represented by the following formulas (101) to (191). These groups may further have a substituent.

[0291]

[0292]

[0293]

[0294]

[0295] 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.

[0296] In the polymer compound that is a p-type semiconductor material, the polymer compound that is a p-type semiconductor material may include, as a structural unit, a structure in which the structural unit represented by formula (3) and the structural unit represented by formula (4) already described are linked together.

[0297] 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).

[0298] 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 the following formula (5).

[0299]

[0300] In formula (5), Ar ６ represents an arylene group.

[0301] Ar ６ The arylene group represented by the formula (I) means an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon also includes a compound having a fused ring and a compound in which two or more rings selected from the group consisting of independent benzene rings and fused rings are bonded together directly or via a divalent group such as a vinylene group.

[0302] Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as those exemplified as the substituent that the heterocyclic compound may have.

[0303] Ar ６ The number of carbon atoms of the arylene group represented by the formula (I) is preferably 6 to 60, not including the number of carbon atoms of the substituent, and more preferably 6 to 20. The number of carbon atoms of the arylene group including the substituent is preferably 6 to 100.

[0304] Ar ６ Examples of the arylene group represented by the formula (I) include a phenylene group (e.g., Formulas 1 to 3 below), a naphthalene-diyl group (e.g., Formulas 4 to 13 below), an anthracene-diyl group (e.g., Formulas 14 to 19 below), a biphenyl-diyl group (e.g., Formulas 20 to 25 below), a terphenyl-diyl group (e.g., Formulas 26 to 28 below), a fused ring compound group (e.g., Formulas 29 to 35 below), a fluorene-diyl group (e.g., Formulas 36 to 38 below), and a benzofluorene-diyl group (e.g., Formulas 39 to 46 below).

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313] In the formula, R is defined as C ６０ The definition of R is the same as that of the fullerene derivative. Multiple Rs may be the same or different.

[0314] The constitutional unit represented by formula (5) is preferably a constitutional unit represented by the following formula (5-1) or formula (5-2).

[0315]

[0316] In the formula (5-1) and the formula (5-2), R is defined as C ６０ The definition of R is the same as that of R in the formula of the fullerene derivative. The two R may be the same or different.

[0317] 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.

[0318] 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%, and from the viewpoint of improving the charge transport property as a p-type semiconductor material, is more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%, when the amount of all constitutional units contained in the polymer compound is taken as 100 mol%.

[0319] Specific examples of polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas (P-1) to (P-21).

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330] In the above formula, R is defined as C ６０ The definition of R is the same as that of the fullerene derivative. Multiple Rs may be the same or different.

[0331] 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.

[0332] <Combination of p-Type Semiconductor Material and n-Type Semiconductor Material> The composition of the present disclosure preferably employs, as the p-type semiconductor material, a polymer compound containing at least one selected from the group consisting of the structural unit represented by the above-described formula (3) and the structural unit represented by the above-described formula (4), and, as the n-type semiconductor material, a compound represented by the above-described formula (1), wherein in formula (1), D's are each independently a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds by the shortest distance contains four or more double bonds, L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds by the shortest distance contains three or less double bonds, L2 does not have the same chemical structure as D and is an aromatic group having two bonds, n is 1 or 2, m is 0 or 1, and n+m=2, and A1 and A2 are acceptor groups containing a quinoxaline skeleton. The combination of the p-type semiconductor material and the n-type semiconductor material enables the composition to reduce the dark current in the photoelectric conversion element and further provides a high D ＊ It is possible to provide a photoelectric conversion element that exhibits D ＊ is the specific detectability, and is an index that indicates that the larger the value, the higher the light detectability and the more excellent the resolution.

[0333] The quinoxaline skeleton in A1 and A2 may have a carbon atom substituted with another atom. The acceptor groups (A1 and A2) containing a quinoxaline skeleton are preferably each independently any one of the groups represented by the following formulae (a-5) to (a-8):

[0334]

[0335] In formulas (a-5) to (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.

[0336] Also, high D ＊From the viewpoint of obtaining a photoelectric conversion element exhibiting the formula (3), it is preferable that the p-type semiconductor material has at least one selected from the group consisting of the structural unit represented by formula (3) and the structural unit represented by formula (4) have an aryl group as a substituent within its structure. When the p-type semiconductor material contains a structural unit represented by formula (3), R in the above formulas (Z-1) to (Z-7) represented by Z in formula (3) is preferably an aryl group among the above-mentioned substituents, and is preferably any one of an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, or an optionally substituted cycloalkyl group. When there are multiple R, the multiple R may be the same or different from each other.

[0337] <Ink> The ink of the present disclosure contains a p-type semiconductor material, an n-type semiconductor material, and a solvent, and the n-type semiconductor material preferably contains the compound of the present disclosure. As described above, the composition of the present disclosure contains a p-type semiconductor material and an n-type semiconductor material, and the n-type semiconductor material contains the compound of the present disclosure, so the ink of the present disclosure is preferably an ink for forming an active layer of a photoelectric conversion element, and more preferably an ink for forming a bulk heterojunction active layer.

[0338] According to the ink of the present disclosure, by containing a p-type semiconductor material and the compound of the present disclosure, it is possible to reduce dark current in a photoelectric conversion element.

[0339] Furthermore, according to the ink of the present disclosure, it is preferable to use a polymer compound containing at least one selected from the group consisting of the structural unit represented by the above-mentioned formula (3) and the structural unit represented by the above-mentioned formula (4) as the p-type semiconductor material, and a compound represented by the above-mentioned formula (1) as the n-type semiconductor material, wherein in formula (1), D each independently represents a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds, L1 and L1' each independently represents an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds, L2 does not have the same chemical structure as D but is an aromatic group having two bonds, n is 1 or 2, m is 0 or 1, and n + m = 2, and A1 and A2 are acceptor groups containing a quinoxaline skeleton. This combination of p-type and n-type semiconductor materials enables the ink to reduce dark current in a photoelectric conversion element and to exhibit a high D ＊ It is possible to provide a photoelectric conversion element that exhibits the following.

[0340] The quinoxaline skeleton in A1 and A2 may have a carbon atom substituted with another atom. The acceptor groups (A1 and A2) containing a quinoxaline skeleton are preferably each independently a group represented by any one of the above formulae (a-5) to (a-8).

[0341] Also, high D ＊ From the viewpoint of obtaining a photoelectric conversion element exhibiting the above, preferred aspects of the p-type semiconductor material are the same as the preferred aspects of the p-type semiconductor material described above in <Combination of p-type semiconductor material and n-type semiconductor material>.

[0342] The solvent may be, for example, a mixed solvent that combines a first solvent and a second solvent, which will be described later. 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.

[0343] The first solvent and second solvent that can be suitably used in the ink for forming the active layer and their combinations will be described below.

[0344] <First Solvent> The first solvent is preferably a solvent capable of dissolving a p-type semiconductor material. The first solvent is preferably an aromatic hydrocarbon.

[0345] Examples of aromatic hydrocarbons include toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, trimethylbenzene (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1-chloronaphthalene, bromobenzene, tetralin, and indane.

[0346] The first solvent may be composed of one kind of aromatic hydrocarbon or two or more kinds of aromatic hydrocarbons, but is preferably composed of one kind of aromatic hydrocarbon.

[0347] 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.

[0348] <Second Solvent> The second solvent is preferably selected from the viewpoints 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.

[0349] The second solvent is preferably, for example, acetophenone, propiophenone, butyl benzoate, or methyl benzoate, from the viewpoint of further reducing dark current.

[0350] <Combination of First Solvent and Second Solvent> 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.

[0351] <Mass Ratio of First Solvent and Second Solvent> The mass ratio of the first solvent, which is the main solvent, to the second solvent, which is an 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.

[0352] <Optional Other Solvent> The solvent may contain any other solvent other than the first solvent and the second solvent. When the total mass of all solvents contained in the ink is taken as 100 mass%, the content of the optional other solvent is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less. As the optional other solvent, a solvent having a higher boiling point than the second solvent is preferred.

[0353] 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.

[0354] 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.

[0355] 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.

[0356] 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.

[0357] 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.

[0358] 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.

[0359] 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 obtained mixed solvent, or by adding a p-type semiconductor material to a first solvent, adding an n-type semiconductor material to a second solvent, and then mixing the first solvent and the second solvent to which each material has been added.

[0360] The first and second solvents and the p-type and n-type semiconductor materials may be mixed by heating them to a temperature equal to or lower than the boiling point of the solvent.

[0361] After mixing the first solvent and the second solvent with the p-type semiconductor material and the n-type semiconductor material, 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).

[0362] <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 containing a p-type semiconductor material and an n-type semiconductor material, and it is preferable that the n-type semiconductor material contains the compound of the present disclosure. Preferred aspects of the p-type semiconductor material and the n-type semiconductor material are as described above.

[0363] 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.

[0364] Here, an example of a configuration that the photoelectric conversion element of the present disclosure can take will be described. Fig. 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure.

[0365] 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.

[0366] 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.

[0367] Components that can be included in the photoelectric conversion element of the present disclosure will be specifically described below.

[0368] <Substrate> A photoelectric conversion element is usually formed on a substrate (support substrate). In some cases, the element is further sealed with a 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 does not chemically change, especially when a layer containing an organic compound is formed.

[0369] 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.

[0370] <Electrodes> The photoelectric conversion element includes a pair of electrodes, an anode and a cathode. At least one of the anode and the cathode is preferably a transparent or semi-transparent electrode to allow light to enter.

[0371] Examples of transparent or translucent electrode materials include conductive metal oxide films and translucent 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 translucent electrode materials are 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 translucent electrode may be an anode or a cathode.

[0372] 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 the electrode with low optical transparency include metals and conductive polymers. Specific examples of materials for the electrode 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 alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

[0373] <Active Layer> The active layer included in the photoelectric conversion element according to 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 according to the present disclosure as the n-type semiconductor material.

[0374] 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. 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, particularly from the viewpoint of further reducing dark current. Furthermore, 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.

[0375] <Intermediate Layer> 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.

[0376] 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)).

[0377] As shown in Fig. 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.

[0378] 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.

[0379] The hole transport layer contains a hole transport material. Examples of the hole transport material include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing a structural unit having an aromatic amine residue, CuSCN, CuI, NiO, and tungsten oxide (WO ３ ) and molybdenum oxide (MoO ３ Examples of hole transporting material products include Avantama P-10 and P-21.

[0380] 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.

[0381] The photoelectric conversion element of the present disclosure preferably has a configuration in which the intermediate layer is an electron transport layer, and a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are stacked in this order so as to be in contact with each other.

[0382] As shown in Fig. 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.

[0383] The electron transport layer provided in contact with the cathode is sometimes referred to as 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.

[0384] 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.

[0385] 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 a conventional manner, and polymers obtained by chemically modifying these by reacting them with various compounds. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

[0386] 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.

[0387] Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a zinc-containing metal oxide is preferred, and zinc oxide is 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.

[0388] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0389] <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. An example of the sealing member is a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV-curable resin.

[0390] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0391] The sealing layer is preferably formed from a material having a moisture-blocking property (water vapor barrier property) or an oxygen-blocking property (oxygen barrier property). Suitable examples of the sealing layer material include organic materials such as trifluoroethylene, 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.

[0392] 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.

[0393] <Dark Current> The dark current of the sealed photoelectric conversion element containing the compound of the present disclosure was 80 μA / cm ２ Preferably, 50 μA / cm or less ２ More preferably, 20 μA / cm or less ２ More preferably, 10 μA / cm or less ２ More preferably, 8 μA / cm or less ２ The following is even more preferable: When the photoelectric conversion element is used as a light detection element, the dark current is preferably as small as possible from the viewpoint of detection sensitivity.

[0394] Dark current is measured, for example, by the following method. 0.56% by mass of the target compound to be measured, 0.8% by mass of polymer compound P-1 (described below), 0.24% by mass of PCBM (described below), and the remaining amount of solvent (a mixed solvent of chloroform and 1-chloronaphthalene (mixing ratio chloroform / 1-chloronaphthalene = 97 wt % / 3 wt %)) to make up 100% by mass of the ink as a whole are mixed and stirred at 60°C for 8 hours. The resulting mixture is filtered using a filter to obtain an ink.

[0395] A glass substrate on which a thin film of ITO (anode) is formed to a thickness of 45 nm by sputtering is prepared, and this glass substrate is subjected to ozone UV treatment as a surface treatment.

[0396] Next, a solution prepared by diluting 80% ethoxylated polyethyleneimine aqueous solution (manufactured by Sigma-Aldrich, 37% by mass aqueous solution) 500 times with water 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 the air at 120°C for 10 minutes to form an electron transport layer.

[0397] Next, the ink thus obtained is applied to the electron transport layer by spin coating to form a coating film, which is then dried by heating for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-baking step), and then heated for 10 minutes at 100°C on a hot plate in a nitrogen atmosphere (post-baking step) to form an active layer with a thickness of approximately 350 nm.

[0398] Next, molybdenum oxide (MoO ３ ) layer is formed to a thickness of about 30 nm to serve as a hole transport layer.

[0399] Next, a silver (Ag) layer is formed on the formed hole transport layer to a thickness of about 60 nm to serve as a cathode. Through the above steps, a photoelectric conversion element is manufactured on the glass substrate.

[0400] Next, a UV-curable sealant is applied to the periphery of a glass substrate serving as a sealing substrate, and the glass substrate serving as a sealing substrate is attached to the center of the glass substrate serving as a support substrate. After this, UV light is irradiated to seal the photodetector in the gap between the support substrate and the sealing substrate, thereby obtaining a sealed photoelectric conversion element. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction is a 2 mm x 2 mm square. The resulting sealed element is used as a sample.

[0401] For the sample manufactured as described above, a voltage of −10 V to 2 V is applied to the sealed body of the photodetector in a dark state where no light is irradiated, and the current value when a reverse bias voltage of −3 V is applied, measured using a known method, is obtained as the dark current (Jd).

[0402] <Applications of Photoelectric Conversion Element> Applications of the photoelectric conversion element of the present disclosure include photodetection elements and solar cells. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from the transparent or semitransparent electrode side while applying a voltage (reverse bias voltage) between the electrodes, and can operate as a photodetection element (photosensor). Furthermore, by integrating a plurality of photodetection elements, the element can also be used as an image sensor. In this way, the photoelectric conversion element of the present disclosure can be particularly suitably used as a photodetection element.

[0403] 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.

[0404] 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.

[0405] 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.

[0406] 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.

[0407] <Method for 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.

[0408] Hereinafter, a method for manufacturing a photoelectric conversion element having a structure 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 one another in this order will be described.

[0409] (Substrate Preparation Step) 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 may be purchased from the market, and the conductive thin film may be patterned to form an anode, as necessary, to prepare a support substrate provided with an anode.

[0410] In the method for producing a photoelectric conversion element according to the present disclosure, the method for forming an anode on a supporting substrate is not particularly limited. The anode can be formed on a structure where the anode is to be formed (e.g., a supporting substrate, an active layer, a hole transport layer) by any suitable conventional method such as vacuum deposition, sputtering, ion plating, plating, or coating using the materials already described.

[0411] (Step of Forming Hole Transport Layer) 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.

[0412] The method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process for forming the hole transport layer, it is preferable to form the hole transport layer by any suitable coating method known in the art. 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 as already described, or by a vacuum deposition method.

[0413] (Active Layer Forming Process) In the method for producing a photoelectric conversion element according to 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 forming process. The active layer is preferably produced by a coating method using an ink (coating liquid). Preferred aspects of the ink are as described above.

[0414] Hereinafter, steps (i) and (ii) included in the process of forming the active layer, which is a main component of the present disclosure, will be described.

[0415] Step (i) Any suitable coating method can be used as a method for applying the ink to a coating target. As the coating method, slit coating, knife coating, spin coating, microgravure coating, gravure coating, bar coating, inkjet printing, nozzle coating, or capillary coating is preferred, slit coating, spin coating, capillary coating, or bar coating is more preferred, and slit coating or spin coating is even more preferred.

[0416] 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 far left is formed first, the target to which the ink for forming an active layer is applied is 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 far left is formed first, the target to which the ink for forming an active layer is applied is the electron transport layer.

[0417] Step (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 under an inert gas atmosphere such as nitrogen gas, hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

[0418] 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).

[0419] The step of forming the active layer may include other steps in addition to the steps (i) and (ii), provided that the other steps do not impair the object and effect of the present disclosure.

[0420] The method for producing a photoelectric conversion element according to the present disclosure may be a method for producing a photoelectric conversion element including a plurality of active layers, or may be a method in which step (i) and step (ii) are repeated a plurality of times.

[0421] The method for manufacturing a photoelectric conversion element according to the present disclosure includes a step of forming an electron transport layer (electron injection layer) provided on an active layer.

[0422] The method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process for forming the electron transport layer, it is preferable to form the electron transport layer by any suitable conventional vacuum deposition method.

[0423] (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-described process.

[0424] (Sealed body forming process) When forming 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 material are bonded together without any gaps. 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 irradiation with UV light, thereby obtaining a sealed photoelectric conversion element.

[0425] <Photodetector> As described above, the photoelectric conversion element of the present disclosure, particularly the photodetector (optical sensor), can function by being incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device).

[0426] Examples are provided below to further explain the present disclosure, but the present disclosure is not limited to the examples described below.

[0427] A photoelectric conversion element was fabricated using a p-type semiconductor material and an n-type semiconductor material.

[0428] <p-type semiconductor material> As polymer compound P-1, a material synthesized with reference to the method described in WO 2011 / 052709 was used. As polymer compound P-2, a material synthesized with reference to the method described in WO 2013 / 051676 was used. As polymer compound P-19, a product manufactured by 1-material, trade name: PCE-10, was purchased commercially and used. As polymer compound P-20, a product manufactured by 1-material, trade name: PM-6, was purchased commercially and used. As polymer compound P-21, a material synthesized by the method described below was used.

[0429] (Polymer compound P-1)

[0430]

[0431] (Polymer compound P-2)

[0432]

[0433] (Polymer compound P-19)

[0434]

[0435] (Polymer compound P-20)

[0436]

[0437] (Polymer compound P-21)

[0438]

[0439] <N-type Semiconductor Material> The following compound was used as the n-type semiconductor material, the synthesis method of which will be described later.

[0440] (Compound N-1)

[0441]

[0442] (Compound N-2)

[0443]

[0444] (Compound N-3)

[0445]

[0446] (Compound N-4)

[0447]

[0448] (Compound N-5)

[0449]

[0450] (Compound N-6)

[0451]

[0452] (Compound N-7)

[0453]

[0454] (Compound N-8)

[0455]

[0456] (Compound N-9)

[0457]

[0458] (Compound N-10)

[0459]

[0460] (Compound N-11)

[0461]

[0462] (Compound RN-1)

[0463]

[0464] (Compound RN-2)

[0465]

[0466] (Synthesis of Compound N-1) Compound 2 was synthesized using Compound 1.

[0467]

[0468] In a 300 mL four-neck flask, 3-methoxythiophene (Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH.H ２O (0.833 g, 4.38 mmol) and toluene (100 g) were charged, purged with nitrogen, and then 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 completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane = 100 wt%) to obtain 13.4 g of compound 2 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 2 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)

[0469] Compound 3 was synthesized using compound 2.

[0470]

[0471] A 200 mL four-neck flask was charged with compound 2 (4.0 g, 12.3 mmol) and THF (45 mL), and the flask was 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 flask was maintained at an internal temperature of -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 the flask was gradually added dropwise to a reaction mass whose internal temperature was -65°C. After completion of the dropwise addition, the flask was maintained at an internal temperature of -65°C for 1 hour, then heated to room temperature, and stirred for 2 hours. After quenching by pouring in 20% aqueous ammonium chloride solution (26 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 5.91 g of compound 3 as a crude product. The NMR spectrum of the resulting compound 3 was analyzed. The results are as follows. １H-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)

[0472] Compound 4 was synthesized using compound 3.

[0473]

[0474] A 500 mL four-neck flask was charged with crude compound 3 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and THF (149 mL), and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.600g, 0.655mmol), P(tBu ３ ) HBF ４ (0.399g, 1.38mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with an aqueous solution (60.6 g) and then heated to 65°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then 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 3.72 g of compound 4 as a yellow-brown liquid. The NMR spectrum of the resulting 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)

[0475] Compound 5 was synthesized using compound 4.

[0476]

[0477] A 100 mL four-neck flask was charged with compound 4 (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 5 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)

[0478] Compound 7 was synthesized using compound 6.

[0479]

[0480] 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), and after purging with nitrogen, the flask was cooled to -73°C. nBuLi (1.56 mol / L in hexane, 1.75 mL, 2.73 mmol) was then charged, and the flask was kept at an internal temperature of -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 charged into a dropping funnel and added dropwise little by little to the reaction mass at an internal temperature of -65°C. After completion of the addition, the internal temperature was maintained at -65°C for 1 hour, then the temperature was raised to room temperature and stirred for 1 hour. After quenching by pouring 20% ​​aqueous ammonium chloride solution (5.3 mL), the aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then totally concentrated using a rotary evaporator to obtain 1.49 g of crude compound 7.

[0481] Compound 8 was synthesized using Compound 7 and Compound 5.

[0482]

[0483] A 100 mL four-neck flask was charged with crude compound 7 (1.49 g), compound 5 (2.05 g, 3.20 mmol), and THF (29.6 g), and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.113g, 0.123mmol), P(tBu ３ ) HBF ４ (0.0749g, 0.258mmol), 3mol / L of K ３ P.O. ４The mixture was charged with toluene and then an aqueous solution (11.4 g) of toluene, and then heated 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 using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 1.27 g of compound 8 as a red liquid. The NMR spectrum of the resulting compound 8 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.20 (1H), 7.13-7.10 (m, 2H), 6.93-6.91 (m, 1H), 4.10 (2H), 4.05 (2H), 1.93-0.57 (m, 80H)

[0484] Compound 9 was synthesized using compound 8.

[0485]

[0486] In a 50 mL four-neck flask, compound 8 (1.25 g, 1.30 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.497 g, 1.56 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and Pd(OAc) were placed. ２ (0.0364g, 0.162mmol), [(tBu) ２ MePH]BF ４ (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), K ２ CO ３(0.538 g, 3.89 mmol) and DMF (12.5 g) were charged and nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 120°C and stirred for 5 hours. After cooling to room temperature, it was diluted with toluene and washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.620 g of compound 9 as a deep red-purple liquid. The NMR spectrum of the obtained compound 9 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.74 (1H), 7.47 (2H), 7.32 (1H), 7.20 (1H), 7.12 (1H), 4.13 -4.06 (m, 6H), 1.89-0.60 (m, 95H)

[0487] Compound 9 was used to synthesize compound N-1.

[0488]

[0489] In a 50 mL four-neck flask, compound 9 (0.600 g, 0.499 mmol), compound 10 (0.366 g, 1.50 mmol) synthesized according to the method described in WO 2020 / 109823, p-TsOH·H ２ O (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), MgSO ４ (0.300 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.632 g (yield 78%) of compound N-1 as a black solid. The NMR spectrum of the obtained compound N-1 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 8.98-8.95 (m, 2H), 8.76-8.72 (m, 2H), 8.14-8.11 (m, 2H), 7.74 (1H), 7.50-7.32 (m, 4H), 4.19 (6H), 2.06-0.64 (m, 95H)

[0490] (Synthesis of Compound N-2) Compound 11 was synthesized using Compound 2.

[0491]

[0492] A 1 L four-neck flask was charged with compound 2 (15.35 g, 47.3 mmol) and THF (460.5 g), and the flask was purged with nitrogen and then cooled to 0 °C. NBS (8.33 g, 46.8 mmol) was added and stirred at 0 °C. After stirring for 2 hours, 3% aqueous sodium sulfite solution (249 g) was added 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: hexane) to obtain 18.53 g of compound 11 as a colorless liquid.

[0493] Compound 12 was synthesized using compound 11.

[0494]

[0495] A 3 L four-neck flask was charged with compound 11 (92.28 g, 228.7 mmol) and THF (1038 mL), and the flask was purged with nitrogen and then cooled to -73 °C. LDA (1 M in THF / Hexane, 228.7 mL, 228.7 mmol) was slowly added dropwise, and after completion of the addition, the mixture was kept at an internal temperature of -73 °C for 2 hours. DMF (35.3 mL, 457.4 mmol) was slowly added dropwise to the reaction mass at an internal temperature of -73 °C, and after completion of the addition, the mixture was warmed to room temperature and stirred for 2 hours. After quenching by pouring 20% ​​aqueous ammonium chloride solution (489 mL), the aqueous layer was removed from the resulting mass by liquid separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 70 / 1 (volume ratio)) to obtain 45.00 g of compound 12 as a yellow liquid. The NMR spectrum of the obtained compound 12 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.70 (1H), 7.37 (1H), 3.95 (2H), 1.80-1.72 (m, 1H), 1.57-1.27 (m, 24H), 0.90-0.86 (m, 6H)

[0496] Compound 13 was synthesized using compound 8.

[0497]

[0498] In a 50 mL four-neck flask, compound 8 (0.96 g, 1.0 mmol), 5-Bromo-4-((2-octhlyldecyl)oxy)thiophene-2-carb aldehyde (0.864 g, 1.2 mmol), and Pd(OAc) were placed. ２ (0.168g), [(tBu) ２ MePH]BF ４ (0.099 g), pivalic acid (0.102 g), K ２ CO ３(0.415 g) and DMF (9.5 g) were charged and nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 110 °C and stirred for 7 hours. After cooling to room temperature, it was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.28 g of compound 13. 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.73 (1H), 7.46 (2H), 7.33 (1H), 7.20 (1H), 7.12 (1H), 4.12 -4.06 (m, 6H), 1.89-0.60 (m, 111H)

[0499] Compound 13 was used to synthesize compound N-2.

[0500]

[0501] In a 50 mL four-neck flask, compound 13 (0.28 g), compound 10 (0.15 g) synthesized according to the method described in WO 2020 / 109823, p-TsOH·H ２ 0 (0.12 g), EtOH (2.5 g), toluene (5.6 g), MgSO ４ (0.14 g) was charged and kept warm in an oil bath heated to 50 °C. After stirring for 1 hour, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.22 g (yield 59%) of compound N-2 as a black solid. The NMR spectrum of the obtained compound N-2 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 8.99-8.96 (m, 2H), 8.77-8.72 (m, 2H), 8.15-8.11 (m, 2H), 7.74 (1H), 7.50-7.33 (m, 4H), 4.21-4.18 (m, 6H), 1.98-0.63 (m, 111H)

[0502] (Synthesis of Compound N-3) Compound 14 was synthesized using Compound 3.

[0503]

[0504] A 200 mL four-neck flask was charged with crude compound 3 (5.52 g), compound 12 (5.29 g), and THF (50 g), and nitrogen was bubbled through for 30 minutes. ２ (dba) ３ (0.561g), P(tBu ３ ) HBF ４ (0.373g), 3mol / L K ３ P.O. ４ The mixture was charged with an aqueous solution (22.7 g) and then heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 100 to 50 / 5 (volume ratio)) to obtain 7.55 g of crude compound 14 as a yellowish-brown liquid. １ H NMR (300MHz, CDCl3) δ9.75(s, 1H), 7.46(s, 1H), 7.08(d, 1H), 6.28(d, 1H), 4.04(d, 2H)m, 3.83( d, 2H), 1.85-1.27 (m, 44H), 0.90-0.86 (m, 12H)

[0505] Compound 15 was synthesized using compound 14.

[0506]

[0507] Compound 14 (6.70 g) and chloroform (133 g) were charged into a 100 mL four-neck flask, and the atmosphere was replaced with nitrogen using a nitrogen flow. The flask was then cooled to 0°C using an ice bath. NBS (1.75 g) was then charged. After stirring for 1 hour, water was added and the temperature was raised to room temperature. The organic layer was extracted, washed once with water and once with saturated brine, dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 100 to 95 / 5 (volume ratio)), yielding 6.98 g of crude compound 15 as a yellowish-brown liquid. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.77 (s, 1H), 7.45 (s 1H), 7.02 (s, 1H), 4.05 (d, 2H), 3.93 (d, 2H), 1.89-1.27 (m, 44H), 0.93-0.86 (m, 12H)

[0508] Compound 16 was synthesized using compound 15.

[0509]

[0510] A 100 mL four-neck flask was charged with crude compound 7 (2.99 mmol), compound 15 (3.89 mmol), and THF (36.1 g), and nitrogen was bubbled through the flask for 30 minutes. ２ (dba) ３ (0.137g, 0.150mmol), P(tBu ３ ) HBF ４ (0.0913g, 0.315mmol), 3mol / L K ３ P.O. ４ The mixture was then charged with toluene and an aqueous solution (13.9 g) of 1,000 sucrose, followed by heating 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. Half of the obtained crude product was purified by recycling GPC to obtain 0.930 g of compound 16 as a red liquid. The NMR spectrum of the obtained compound 16 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ9.75 (1H), 7.44 (1H), 7.13 (1H), 7.12 (2H), 6.93 (1H), 4.04-4.10 (4H), 1.88 (6H), 0.57-1.60 (m, 90H)

[0511] Compound 17 was synthesized using compound 16.

[0512]

[0513] Compound 16 (0.761 g, 0.707 mmol) and chloroform (7.61 g) were added to a 50 ml four-neck flask. Under cooling in an ice bath, N-bromosuccinimide (0.126 g, 0.707 mmol) was added in three portions. After stirring for 30 minutes, 3% aqueous sodium sulfite solution (3.8 g) was added and the temperature was raised to room temperature. The mixture was diluted with chloroform and separated twice with water. It was then dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was passed through a short column (heptane / ethyl acetate = 10 / 1) to obtain 0.891 g of compound 17. The NMR spectrum of the resulting compound 17 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.75 (1H), 7.44 (1H), 7.19 (1H), 7.08 (1H), 6.94 (1H), 4. 03-4.10 (4H), 1.84 (6H), 0.58-1.84 (m, 90H)

[0514] Compound 19 was synthesized using compound 18.

[0515]

[0516] A 100 ml four-neck flask was purged with nitrogen and charged with Compound 18 (1.00 g, 4.11 mmol, manufactured by Frontier Scientific), bis-pinacolatodiboron (1.57 g, 6.17 mmol), and Pd(dppf)Cl. ２(0.151 g, 0.206 mmol), potassium acetate (1.21 g, 12.3 mmol), and cyclopentyl methyl ether (20.0 g) were added, and the mixture was heated to 100°C. After stirring for 2 hours, the reaction mass was cooled to room temperature and filtered through Celite while washing with toluene. The filtrate was washed with water and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the mixture was completely concentrated using an evaporator, yielding 1.26 g of crude compound 19. The NMR spectrum of the obtained compound 19 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ10.83 (1H), 8.33 (1H), 8.20 (1H), 1.26 (12H)

[0517] Compound 20 was synthesized using compound 17 and compound 19.

[0518]

[0519] Compound 17 (0.792 g, 0.686 mmol), compound 19 (0.298 g, 1.03 mmol), and THF (18.0 g) were placed in a 50 mL four-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.314g, 0.0342mmol), P(tBu ３ ) HBF ４ (0.0209g, 0.0720mmol), 3mol / L of K ３ P.O. ４ The mixture was then charged with an aqueous solution (3.17 g) and then heated 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 to obtain 0.952 g of crude compound 20. The NMR spectrum of the crude compound 20 obtained was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ10.68 (1H), 9.78 (1H), 8.26 (1H), 8.19 (1H), 7.92 (1H), 7.46 (1H), 7.22 (1H), 7.15 (1H), 4.10 (4H), 1.80-2.01 (6H), 0.50-1.70 (90H)

[0520] Compound N-3 was synthesized using Compound 20 and Compound 10.

[0521]

[0522] A 100 mL four-neck flask was charged with the crude product of compound 20 (0.850 g), compound 10 (0.558 g, 2.06 mmol) synthesized according to the method described in WO 2020 / 109823, and p-TsOH.H ２ O (0.391 g, 2.06 mmol), EtOH (7.70 g), toluene (17.0 g), MgSO ４ (0.425 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 1.5 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. The filtrate was concentrated using an evaporator and then repulped and washed with methanol to obtain a crude product. The obtained crude product was purified by recycling GPC to obtain 0.102 g of compound N-3 as a black solid. The NMR spectrum of the obtained compound N-3 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ8.94 (2H), 8.70 (1H), 8.58 (2H), 8.10 (2H), 7.50 (2H), 4.15 (4H), 1.95 (6H), 0.64-1.40 (90H)

[0523] (Synthesis of Compound N-4) Compound 21 was synthesized using Compound 8.

[0524]

[0525] Compound 8 (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) were charged into a 100 mL four-neck flask, and after replacing with nitrogen, the internal temperature was raised to 80°C and stirred for 3 hours. After cooling to room temperature, the flask was diluted with 5% K ３ P.O. ４ The mixture was quenched with an aqueous solution. 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 using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 2.20 g of compound 21 as a red liquid (yield 89%). The NMR spectrum of the resulting compound 21 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)

[0526] Compound 22 was synthesized using compound 21.

[0527]

[0528] In a 100 mL four-neck flask, compound 21 (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) were charged and purged with nitrogen. The internal temperature was then raised to 80°C and stirred for 2 hours. 8.48 g of water was charged into a separate 100 ml four-neck flask, and the reaction mass, cooled to room temperature, was added dropwise. The aqueous layer was removed by separation, and the organic layer was dried over magnesium sulfate and then filtered through silica gel. The resulting filtrate was completely concentrated using a rotary evaporator, yielding 1.98 g of compound 22 (yield 84%). The NMR spectrum of the resulting compound 22 was analyzed. 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)

[0529] Compound 22 was used to synthesize compound 24.

[0530]

[0531] Compound 22 (0.70 g, 0.595 mmol), compound 23 (0.28 g, 0.714 mmol, manufactured by ChemShuttle), and THF (17.9 ml) were placed in a 50 mL four-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.027g, 0.030mmol), P(tBu ３ ) HBF ４ (0.018g, 0.063mmol), 3mol / L of K ３ P.O. ４ The mixture was then charged with an aqueous solution (1.9 ml) and heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The reaction mass 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 recycling GPC to obtain 0.82 g of compound 24 (yield 50%). The NMR spectrum of the resulting compound 24 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ9.81 (1H), 8.12 (1H), 7.38 (1H), 7.02 (1H), 6.99 (1H), 6.93 (1H), 5.55 (1H), 4.29 (2H), 4.04 (4H), 3.78 (2H), 3.64 (2H), 1.84-1.94 (7H), 0.55-1.60 (94H)

[0532] Compound 25 was synthesized using compound 24.

[0533]

[0534] A 50 mL four-neck flask was purged with nitrogen and charged with compound 24 (0.39 g, 0.289 mmol), THF (18.5 mL), water (4.5 mL), and trifluoroacetic acid (0.45 mL). The mixture was stirred at room temperature for 3 hours. The reaction mass was diluted with heptane, quenched with a 5% aqueous solution of disodium hydrogen phosphate, and then washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 → 10 / 1 (volume ratio)) to obtain 0.32 g of compound 25 (yield 87%). The NMR spectrum of the resulting compound 25 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.84 (1H), 9.78 (1H), 8.12 (1H), 7.49 (1H), 7.40 (1H), 7.22 (1H), 7.13 (1H), 4.30 (2H), 4.16 (4H), 1.60-1.94 (7H), 0.55-1.60 (88H)

[0535] Compound 25 was used to synthesize compound N-4.

[0536]

[0537] Compound 25 (0.32 g, 0.247 mmol), compound 10 (0.181 g, 0.742 mmol), p-TsOH・H in a 50 mL four-necked flask. ２O (0.141 g, 0.742 mmol), EtOH (3.6 ml), toluene (7.3 ml), MgSO ４ (0.141 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by recycling GPC to obtain 0.342 g (yield 79%) of compound N-4 as a black solid. The NMR spectrum of the obtained compound N-4 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ8.99 (1H), 8.91 (1H), 8.90 (1H), 8.79 (1H), 8.20 (1H), 8.17 (1H), 8.09 (1H), 7.78 (1H), 7.50 (2H), 7.31 (1H), 4.34 (2H), 4.21 (4H), 1.84-1.94 (7H), 0.55-1.60 (88H)

[0538] (Synthesis of Compound N-5) Compound 26 was synthesized using compound 8.

[0539]

[0540] A 50 mL four-neck flask was charged with Compound 8 (2.89 g), 5-Bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (1.34 g), and Pd(OAc). ２ (0.126g), [(tBu) ２ MePH]BF ４ (0.223 g), pivalic acid (0.306 g), K ２ CO ３(1.24 g) and DMF (20 mL) were charged and nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 120 °C and stirred for 1 hour. After cooling to room temperature, it was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 9 / 1 (volume ratio)) to obtain 3.32 g of compound 26.

[0541] Compound 26 was used to synthesize compound N-5.

[0542]

[0543] A 100 mL four-neck flask was charged with compound 26 (1.30 g, 1.10 mmol), compound 10 (0.767 g, 3.14 mmol) synthesized according to the method described in WO 2020 / 109823, and p-TsOH.H ２ O (0.597 g, 1.50 mmol), EtOH (12 g), toluene (26 g), MgSO ４ (0.65 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 1.26 g (yield 70%) of compound N-5 as a black solid. The NMR spectrum of the obtained compound N-5 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.03 (1H), 9.00 (1H), 8.85 (1H), 8.78 (1H), 8.19 (1H), 8.15 (1H), 7.71 (1H), 7.61-7.51 (m, 3H), 7.31 (1H), 4.19 (t, 4H), 2.85 (2H), 0.64-1.99 (m, 95H)

[0544] (Synthesis of Compound RN-1) Compound 27 was synthesized using Compound 6.

[0545]

[0546] In a 50 mL four-neck flask, 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), tBu-bpy (16.0 mg, 0.0596 mmol) were charged and the mixture was purged with nitrogen, after which 15.0 g of cyclohexane was charged and the mixture was kept warm in an oil bath heated to 60°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The cooled mass was poured into water for quenching. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered while passing the liquid through silica gel, and then totally concentrated using a rotary evaporator to obtain 2.30 g of crude compound 27.

[0547] Compound 28 was synthesized using Compound 27 and Compound 5.

[0548]

[0549] Crude compound 27 (1.13 g), compound 5 (1.80 g, 2.81 mmol), and THF (18.2 g) were placed in a 50 mL four-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.0560g, 0.0612mmol), P(tBu ３ ) HBF ４ (0.0372 g, 0.128 mmol), 3 mol / L K ３ P.O. ４The mixture was charged with toluene and then an aqueous solution (5.66 g), and then heated 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 using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 1.19 g of compound 28 as a deep red viscous liquid. The NMR spectrum of the resulting compound 28 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.46 (2H), 7.20 (2H), 7.13 (2H), 4.10 (4H), 4.06 (2H), 1.94-0.61 (m, 126H)

[0550] Compound RN-1 was synthesized using compound 28.

[0551]

[0552] In a 100 mL four-neck flask, compound 28 (1.15 g, 0.754 mmol), compound 10 (0.553 g, 2.26 mmol), and p-TsOH.H ２ O (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), MgSO ４ (0.575 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.890 g (yield 60%) of compound RN-1 as a black solid. The NMR spectrum of the obtained compound RN-1 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 8.94-8.93 (m, 2H), 8.69 (2H), 8.10 (2H), 7.50-7.35 (m, 6H), 4.19-4.15 (m, 8H), 1.94-0.64 (m, 126H)

[0553] (Synthesis of Compound RN-2) Compound 29 was synthesized using compound 27.

[0554]

[0555] Compound 27 (0.775 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.870 g, 2.72 mmol), and THF (7.0 g) were placed in a 50 mL three-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.054g, 0.06mmol), P(tBu ３ ) HBF ４ (0.034g, 0.12mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 0 to 75 / 25 (mass ratio)) to obtain 0.521 g of compound 29 as a reddish-purple viscous liquid. The NMR spectrum of the resulting compound 29 was analyzed. The results are as follows: １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.47 (2H), 7.32 (2H), 4.11 (4H), 1.79-1.96 (m, 6H), 1.37-171 (m, 16H), 0.88-1.02 (m, 28H), 0.60-0.73 (m, 14H)

[0556] Compound RN-2 was synthesized using compound 29.

[0557]

[0558] In a 50 mL four-neck flask, compound 29 (0.521 g, 0.59 mmol), compound 10 (0.434 g, 1.78 mmol), and p-TsOH.H ２ O (0.338 g, 1.78 mmol), EtOH (4.7 g), toluene (10.4 g), MgSO ４ (0.26 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentration using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) and then repulping and washing with acetone to obtain 0.432 g (yield 55%) of compound RN-2 as a blue-green-black solid. The NMR spectrum of the obtained compound RN-2 was 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)

[0559] (Synthesis of Compound N-6) Compound 36 was synthesized according to the following scheme. The NMR spectrum of the obtained compound 36 was analyzed. The results are as follows. １ H-NMR (300 MHz, DMSO-d6) δ 8.36 (1H), 8.18 (1H), 6.05 (1H)

[0560]

[0561] Compound N-6 was synthesized using Compound 26 and Compound 36.

[0562]

[0563] In a 100 mL four-neck flask, compound 26 (0.300 g, 0.25 mmol), compound 36 (0.399 g, 1.26 mmol), and p-TsOH.H ２ O (0.336 g, 1.77 mmol), EtOH (19.5 g), and toluene (8.1 g) were charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The precipitated solid was recovered by filtration and washed with methanol, ethanol, and heptane to obtain a crude product. The obtained crude product was purified by recycling GPC (developing solvent: chloroform = 100 wt%) to obtain 0.297 g of compound N-6 as a black solid. The NMR spectrum of the obtained compound N-6 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ8.90 (s, 1H), 8.73 (s, 1H), 8.48 (m, 1H), 8.42 (s, 1H), 8.32-8.24 (m, 2H), 7.77 (s, 1H), 7.68-7.64 (m, 1H), 7.36-7.24 (m, 3H), 4.25-4.10 (m, 4H), 2.88 (d, 2H), 2.03-0.68 (m, 95H)

[0564] (Synthesis of Compound N-7) Compound 37 was synthesized using compound 3.

[0565]

[0566] A 500 mL four-neck flask was charged with crude compound 3 (7.80 g), 5-bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (5.51 g, 18.1 mmol), and THF (197 mL), and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.792, 0.866 mmol), P(tBu ３ ) HBF ４ (0.527 g, 1.81 mmol), 3 mol / L K ３ P.O. ４The mixture was charged with an aqueous solution (80.1 g) and then heated to 65°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane and washed twice with water, then 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 7.78 g of compound 37 as a brown liquid. The NMR spectrum of the resulting compound 37 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 7.51 (1H), 6.93 (1H), 6.32 (1H), 3.84 (2H), 2.73 (2H), 0.83-1.77 (m, 46H)

[0567] Compound 37 was used to synthesize compound 38.

[0568]

[0569] A 500 mL four-neck flask was charged with compound 37 (6.60 g, 12.0 mmol) and chloroform (231.0 g). The mixture was purged with nitrogen and then cooled to 0°C. NBS (2.12 g, 11.9 mmol) was added and stirred at 0°C. After stirring for 2 hours, water (165.0 g) was added and the mixture was heated 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 = 25 / 1 (volume ratio)) to obtain 5.13 g of compound 38 as a brown liquid. The NMR spectrum of the resulting compound 38 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 7.53 (1H), 6.89 (1H), 3.94 (2H), 2.69 (2H), 0.84-1.77 (m, 46H)

[0570] Compound 39 was synthesized using Compound 7 and Compound 38.

[0571]

[0572] A 200 mL four-neck flask was charged with crude compound 7 (3.00 g), compound 38 (3.19 g, 5.10 mmol), and THF (68.3 g), and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.259g, 0.284mmol), P(tBu ３ ) HBF ４ (0.172g, 0.596mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with an aqueous solution (26.2 g) and then heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / toluene = 1 / 1 (volume ratio)) to obtain 3.37 g of compound 39 as a red liquid. The NMR spectrum of the resulting compound 39 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.82 (1H), 7.54 (1H), 7.10-7.19 (2H), 7.04 (1H), 6.91-6.94 (1H), 4.05 (2H), 2.78 (2H), 0.57-1.94 (m, 80H)

[0573] Compound 40 was synthesized using compound 39 and compound 12.

[0574]

[0575] In a 100 mL four-neck flask, compound 39 (3.35 g, 3.53 mmol), compound 12 (2.13 g, 4.4 mmol), and Pd(OAc) were added. ２ (0.149g, 0.665mmol), [(tBu) ２ MePH]BF ４ (0.263 g, 1.06 mmol), pivalic acid (0.361 g, 3.53 mmol), K ２ CO ３(1.46 g, 10.6 mmol) and DMF (33.5 g) were charged and nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 120°C and stirred for 1 hour. After cooling to room temperature, it was diluted with heptane and washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 3.53 g of compound 40 as a reddish-purple liquid. The NMR spectrum of the obtained compound 40 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 9.74 (1H), 7.54 (1H), 7.46 (1H), 7.33 (1H), 7.14 (1H), 7.04 (1H), 4.06 -4.09 (m, 4H), 2.79 (2H), 0.60-1.90 (m, 111H)

[0576] Compound N-7 was synthesized using compound 40 and compound 10.

[0577]

[0578] In a 50 mL four-neck flask, compound 40 (1.001 g, 0.770 mmol), compound 10 (0.564 g, 2.311 mmol), and p-TsOH.H ２ O (0.440 g, 2.311 mmol), EtOH (9.0 g), toluene (20.0 g), and magnesium sulfate (0.500 g) were charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The magnesium sulfate was removed by filtration, and the filtrate was concentrated. Methanol (20 g) was added to the concentrate, and the mixture was stirred at room temperature for 10 minutes. After filtration and drying, a crude product was obtained. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform). The column-purified product was dissolved in chloroform (5 g), and heptane (5 g) was added at room temperature to cause crystallization. The mixture was then filtered and dried to obtain 0.207 g of compound N-7. The NMR spectrum of the obtained compound N-7 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ9.05 (s, 1H), 8.95 (s, 1H), 8.88 (s, 1H), 8.72 (br, 1H), 8.22 (s, 1H) 8.11 (s, 1H), 7.75 (m, 1H), 7.71 (s, 1H), 7.38-7.31 (br, 3H), 4.21-4.17 (m, 4H), 2.87 (d, 2H), 1.99-0.63 (m, 111H)

[0579] (Synthesis of Compound N-8) Compound N-8 was synthesized using Compound 40 and Compound 36.

[0580]

[0581] In a 100 mL four-neck flask, compound 40 (0.272 g, 0.210 mmol), compound 36 (0.330 g, 1.04 mmol), and p-TsOH.H ２ O (0.279 g, 1.46 mmol), EtOH (17.7 g), and toluene (7.4 g) were charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature, filtered, and washed with methanol to obtain a crude product. The obtained crude product was purified by recycled GPC (developing solvent: chloroform). 0.25 g of the obtained recycled GPC purified product was dissolved in chloroform (4.0 g), and methanol (17.5 g) was added at room temperature to cause crystallization, followed by filtration and drying to obtain 0.240 g of compound N-8. The NMR spectrum of the obtained compound N-8 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 8.93 (1H), 8.79 (1H), 8.38-8.48 (4H), 7.75-7.78 (2H), 7.27-7.43 (3H), 4.20 (4H), 2.88 (4H), 0.65-2.01 (111H)

[0582] (Synthesis of Compound N-9) Compound 41 was synthesized using Compound 1.

[0583]

[0584] A 200 ml four-neck flask was purged with nitrogen, and pTsOH monohydrate (0.42 g, 2.19 mmol), 2-ethyl-1-hexanethiol (9.42 ml, 54.7 mmol), compound 1 (2.16 ml, 21.9 mmol), and toluene (43.2 ml) were added, followed by stirring at 100°C for 2.5 hours. After allowing to cool to room temperature, the mixture was washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane), yielding 4.05 g of compound 41. The NMR spectrum of the obtained compound 41 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.31 (1H), 7.08 (1H), 7.00 (1H), 2.84 (2H), 1.20-1.55 (9H), 0.83-0.95 (6H)

[0585] Compound 42 was synthesized using compound 41.

[0586]

[0587] A 200 ml four-neck flask was purged with nitrogen, and Compound 41 (1.99 g, 8.76 mmol) and chloroform (21.1 ml) were added. The flask was cooled in an ice bath, and N-bromosuccinimide (1.50 g, 8.42 mmol) was added in three portions. After stirring for 4 hours, 3% Na ２ SO ３ The mixture was quenched with an aqueous solution, warmed to room temperature, and the aqueous layer was removed. After washing with water once, the organic layer was dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product. The crude product obtained was dissolved in heptane, filtered through a 10 mm layer of silica gel in a Kiriyama funnel, and concentrated again to obtain 2.45 g of compound 42. The NMR spectrum of the obtained compound 42 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ7.25 (1H), 6.93 (2H), 2.83 (2H), 1.20-1.55 (9H), 0.83-0.95 (6H)

[0588] Compound 43 was synthesized using compound 27 and compound 11.

[0589]

[0590] A 100 mL four-neck flask was purged with nitrogen, and Compound 27 (1.375 g, 2.10 mmol), Compound 11 (1.86 g, 4.62 mmol), and THF (30.9 ml) were added. After bubbling with nitrogen for 30 minutes, Pd ２ (dba) ３ (0.096g, 0.11mmol), [(tBu) ３ PH]BF ４ (0.061g, 0.21mmol), 3M K ３ P.O. ４ An aqueous solution (7.00 ml) was added, and the temperature was raised to 60°C. After keeping the temperature for 1 hour, the reaction solution was cooled to room temperature, diluted with 25 ml of heptane, and washed twice with 12.5 ml of water. The solution was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 9 / 1 (v / v)) to obtain 2.15 g of compound 43 as a red liquid. The NMR spectrum of the obtained compound 43 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.08 (2H), 6.99 (2H), 6.84 (2H), 4.01 (4H), 1.84 (4H), 0.50-1.60 (H)

[0591] Compound 44 was synthesized using compound 43.

[0592]

[0593] A 300 ml four-neck flask was purged with nitrogen, and compound 43 (5.93 g, 5.66 mmol) and THF (66.8 ml) were added. The mixture was then cooled to an internal temperature of -78°C in a dry ice / acetone bath. A 1.6 M nBuLi hexane solution (4.17 ml, 6.51 mmol) was added dropwise, followed by stirring for 1 hour. A THF (33.4 ml) solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.58 g, 8.50 mmol) was prepared and added dropwise over 20 minutes. After the addition, the mixture was stirred at -78°C for 1 hour, warmed to room temperature, and left overnight. The reaction vessel was cooled in an ice bath and quenched with 20% aqueous ammonium chloride solution (12.1 ml). The reaction solution was diluted with heptane, the aqueous layer was removed, and the mixture was separated and washed twice with water. The organic layer was dried over magnesium sulfate, filtered, and then concentrated using an evaporator to obtain 5.89 g of a crude product of Compound 44.

[0594] Compound 45 was synthesized using compound 42 and compound 44.

[0595]

[0596] Compound 42 (0.524 g, 1.70 mmol), the crude product of Compound 44 (3.83 g), and tetrahydrofuran (51.3 ml) were placed in a 100 mL four-neck flask, and the flask was purged with nitrogen. ２ (dba) ３ (0.0781g, 0.085mmol manufactured by Strem Chemicals), [(tBu) ３ PH]BF ４ (Tokyo Chemical Industry Co., Ltd., 0.0495 g, 0.171 mmol), 3M K ３ P.O. ４An aqueous solution (5.7 ml) was charged and heated to 60°C. After stirring and maintaining the temperature for 1 hour, the reaction solution was cooled to room temperature, diluted with heptane, and washed twice with water. The solution was dried over magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified using a silica gel column (developing solvent: heptane → heptane / ethyl acetate = 10 / 1 (v / v)) to obtain 1.19 g of compound 45 as an orange oil. The NMR spectrum of the obtained compound 45 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.10-7.17 (3H), 7.08 (1H), 7.03 (2H), 6.84 (1H), 4.00-4.06 (4H), 2.85 (2H), 1.85 (6H), 0.50-1.65 (105H)

[0597] Compound 46 was synthesized using compound 45.

[0598]

[0599] In a 50 mL four-neck flask, compound 45 (1.04 g, 0.823 mmol), CHCl ３ (10.0 ml) was added and the atmosphere was replaced with nitrogen, (Chloromethylene) dimethylmininium chloride (Tokyo Chemical Industry Co., Ltd., 0.969 g, 7.57 mmol) was added, the temperature was raised to 60 ° C, and the mixture was stirred while keeping the temperature. After stirring for 5 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. Water (4.9 ml), 5 wt% NaHCO ３ The reaction mixture was quenched by pouring 9.9 ml of aq. into the cooled mass while stirring, and the aqueous layer was removed from the resulting mass by separation. The mixture was washed with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain a crude product of compound 46. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (v / v)) to obtain 1.09 g of compound 46 as a reddish-purple oil. The NMR spectrum of the resulting compound 46 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 9.81 (1H), 9.73 (1H), 7.67 (1H), 7.45 (1H), 7.34 (2H), 7.20 (1H), 4.08 (4H), 2.89 (2H), 1.90 (6H), 0.50-1.65 (105H)

[0600] Compound N-9 was synthesized using Compound 46 and Compound 36.

[0601]

[0602] In a 100 mL four-neck flask, compound 46 (0.400 g, 0.301 mmol), compound 36 (0.237 g, 0.752 mmol), and p-TsOH.H ２ O (0.200 g, 1.05 mmol), EtOH (26.0 g), and toluene (10.8 g) were added, and the mixture was kept warm in an oil bath heated to 65°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The precipitated solid was recovered by filtration and washed with methanol, ethanol, and heptane to obtain a crude product. The obtained crude product was purified by recycling GPC (developing solvent: chloroform = 100 wt%) to obtain 0.359 g of compound N-9 as a black solid. The NMR spectrum of the obtained compound N-9 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 8.84 (1H), 8.78 (1H), 8.44 (2H), 8.38 (2H), 7.85 (1H) 7.78 (1H), 7.53 (1H), 7.41 (1H), 7.34 (1H), 4.19 (4H), 3.07 (2H), 2.01 (5H), 0.60-1.85 (104H)

[0603] (Synthesis of Compound N-10) Compound N-10 was synthesized using Compound 46 and Compound 10.

[0604]

[0605] In a 100 mL four-neck flask, compound 46 (0.300 g, 0.23 mmol), compound 10 (0.165 g, 0.68 mmol), and p-TsOH.H ２O (0.129 g, 0.68 mmol), EtOH (3.4 ml), toluene (6.9 ml), MgSO ４ (0.150 g) was charged and replaced with nitrogen, then heated to 65°C and stirred while keeping the temperature. After stirring for 3 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was washed with chloroform while dissolving it. The solution obtained using an evaporator was concentrated, and then washed with methanol using a Kiriyama filter to obtain a crude product. The obtained crude product was purified using recycle GPC to obtain 0.29 g of compound N-10 as a black solid (yield 72%). The NMR spectrum of the obtained compound N-10 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.84 (1H), 9.04 (1H), 8.96 (1H), 8.82 (1H), 8.71 (1H), 8.21 (1H), 8.11 (1H), 7.84 (1H), 7.75 (1H), 7.60 (1H), 7.39 (1H), 7.33 (1H), 4.21 (2H), 4.19 (2H), 3.03 (2H), 1.99-0.5 (118H)

[0606] (Synthesis of Compound N-11) As shown in the following formula, Compound 48 was synthesized using Compound 47.

[0607]

[0608] Compound 47 (Tokyo Chemical Industry Co., Ltd., 1.76 g, 7.0 mmol) and tetrahydrofuran (9.9 ml) were added to a 50 ml four-necked recovery flask. After purging with nitrogen, 1,3-Dibromo-5,5-dimethylhydantoin (Tokyo Chemical Industry Co., Ltd., 1.20 g, 3.5 mmol) was added and the mixture was placed in an oil bath heated to 30°C to maintain the temperature. After stirring for 1 hour, the mixture was removed from the oil bath and allowed to cool to room temperature. 40.8 ml of heptane was added to the reaction mass, and the precipitated solid was removed by filtration. The filtrate was dried over magnesium sulfate, filtered, and then completely concentrated on a rotary evaporator to obtain crude compound 48. The resulting crude product was purified using a silica gel column (developing solvent: heptane) to obtain 1.47 g of compound 48 as a transparent liquid (yield: 63%).

[0609] As shown in the following formula, compound 49 was synthesized using compound 48 and compound 44.

[0610]

[0611] Compound 48 (0.239 g, 0.72 mmol), compound 44 (1.86 g, 0.79 mmol), and tetrahydrofuran (10.7 ml) were placed in a 100 mL four-neck flask, and the flask was purged with nitrogen. ２ (dba) ３ (0.033g, 0.04mmol manufactured by Strem Chemicals), [(tBu) ３ PH]BF ４ (Tokyo Chemical Industry Co., Ltd., 0.021 g, 0.07 mmol), 3M K ３ P.O. ４ An aqueous solution (2.4 ml) was added and heated to 60°C. After stirring at the same temperature for 1 hour, the reaction solution was cooled to room temperature, diluted with heptane (16.5 ml), and washed twice with water (9.5 ml). 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 using a silica gel column (developing solvent: heptane / toluene = 95 / 5 (v / v)) to obtain 0.37 g of compound 49 as a red liquid (yield 40%).

[0612] As shown in the following formula, compound 50 was synthesized using compound 49.

[0613]

[0614] In a 50 mL four-neck flask, compound 49 (0.36 g, 0.28 mmol), CHCl ３ (10.5 ml) was added and replaced with nitrogen, and (chloromethylene) dimethylmininium chloride (Tokyo Chemical Industry Co., Ltd., 0.18 g, 1.40 mmol) was added, and the temperature was raised to 60 ° C. and stirred while keeping the temperature. After stirring for 1 hour, the mixture was removed from the oil bath and allowed to cool to room temperature. Water (14.5 ml), 5 wt % NaHCO ３ The mixture was quenched by pouring 10.5 ml of aq. into the cooled mass with stirring. The aqueous layer was separated from the resulting mass, and the organic layer was washed with 14.5 ml of water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain crude compound 50. The resulting crude product was purified using a silica gel column (developing solvent: heptane / toluene = 7 / 3 (v / v)), yielding 0.24 g of compound 50 as a red liquid (yield 63%).

[0615] Compound N-11 was synthesized using compound 50 and compound 36.

[0616]

[0617] In a 100 mL four-neck flask, compound 50 (0.24 g, 0.18 mmol), compound 36 (0.215 g, 0.44 mmol), p-TsOH·H ２ After bubbling with nitrogen for 30 minutes, the mixture was heated to 65°C and stirred while maintaining the temperature. After 1 hour, Compound 36 (0.106 g, 0.22 mmol), p-TsOH·H ２ O (0.60 g, 0.31 mmol) was added, and the mixture was stirred for another 2 hours while keeping the temperature, and then cooled to room temperature. The precipitated solid was filtered, washed with methanol (24.2 ml), ethanol (24.3 ml), and heptane (23.8 ml) in that order, and air-dried to obtain the crude product. The mobile phase was CHCl ３The resulting fraction was purified by recycling GPC, and the concentrated fraction was washed with methanol using a Kiriyama filtration system. The residue was dried to obtain compound N-11 (yield 81%). The NMR spectrum of the obtained compound N-11 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.16 (1H), 8.80 (1H), 8.51 (1H), 8.46 (1H), 8.42 (1H), 8.39 (1H), 7.78 (1H), 7.46 (1H), 7.33 (1H), 4.20 (4H), 2.97 (4H), 2.00 (4H), 1.9-0.5 (114H)

[0618] (Synthesis of Polymer Compound P-21) Compound 53 was synthesized using Compound 51 and Compound 52.

[0619]

[0620] Magnesium (1.61 g, 0.066 mol), THF (47 g), and iodine (32 mg) were added to a nitrogen-purged 1 L four-neck flask and stirred. After the purple color of the iodine disappeared, a solution of compound 52 (19.8 g, 0.063 mmol) in THF (36 g) was added dropwise to generate a Grignard reagent. A solution containing compound 51 (5.21 g, 0.025 mol) synthesized by the method described in International Publication No. 2011 / 136311 and THF (107 g) was added dropwise to a four-neck flask so that the internal temperature did not exceed 40 °C, obtaining a reaction solution. After stirring for 1 hour, the reaction was stopped by pouring aqueous ammonium chloride into the reaction solution and separating the liquids. The organic layer was dehydrated over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated using a rotary evaporator. The residue was purified by silica gel column chromatography (using hexane and ethyl acetate as the developing solvent) to obtain 14.21 g (20.7 mmol, yield 83%) of Compound 53.

[0621] Compound 53 １The H-NMR measurement results are as follows: δ (ppm): 7.82-7.76 (m, 1H), 7.64 (s, 2H), 7.43 (m, 2H), 7.31 (m, 10H), 7.25 (m, 2H), 7.21 (m, 1H), 7.13 (m, 2H), 6.91 (d, 1H), 6.64 (d, 1H), 6.43 (d, 1H), 3.72-3.64 (m, 1H), 2.63 (t, 4H), 1.61 (m, 4H), 1.22-1.34 (m, 12H), 0.86 (t, 6H).

[0622] Compound 54 was synthesized using compound 53.

[0623]

[0624] A 500 mL four-neck flask was charged with compound 53 (14.21 g, 0.0208 mmol) and heptane (130 g). The atmosphere in the reaction vessel was replaced with nitrogen, and then trifluoroacetic acid (0.409 g, 0.0036 mmol) was added. The mixture was heated to 60°C, stirred for 30 minutes, and then cooled to room temperature to obtain a reaction solution. The reaction solution was washed twice with water, and the organic layer was dehydrated with magnesium sulfate. The mixture was passed through a Kiriyama funnel filled with silica gel, and the filtrate was concentrated using a rotary evaporator to obtain 13.37 g of compound 54 (yield 96.6%).

[0625] Compound 54 １ The H-NMR measurement results are as follows: δ (ppm): 7.73 (s, 2H), 7.64 (s, 2H), 7.45-7.43 (m, 7H), 7.33-7.31 (m, 2H), 7.26 (s, 2H), 7.22 (s, 1H), 7.16-7.13 (m, 1H), 6.93 (d, 1H), 6.65 (d, 1H), 6.44 (d, 1H), 2.64 (t, 4H), 1.67-1.58 (m, 4H), 1.34-1.26 (m, 12H), 0.86 (t, 6H).

[0626] Compound 55 was synthesized using compound 54.

[0627]

[0628] Compound 54 (25.0 g), tetraethylethylenediamine (5.6 mL), and dehydrated tetrahydrofuran (436 mL) were placed in an argon-purged flask and stirred to dissolve. The solution was then cooled to -65°C in a cooling bath containing dry ice and acetone, after which a 1.6 mol / L nBuLi hexane solution (58.9 mL) was added dropwise to the flask and stirred at -65°C for 2 hours. While maintaining the temperature at -65°C, a solution of triisopropoxyborane (19.74 g) dissolved in 40 mL of THF was added dropwise to the flask, and the mixture was stirred at -65°C for an additional hour, after which the temperature was raised to room temperature to obtain a reaction solution. Next, 290 mL of 2% hydrochloric acid was added to the reaction solution, and the mixture was separated. Magnesium sulfate and trimethylolethane (13.5 g) were added to the organic layer, and the mixture was stirred at room temperature for 1 hour. The magnesium sulfate was removed by filtration, and the filtrate was obtained. The solvent was removed from the filtrate under reduced pressure, toluene (700 mL) was added, the precipitated solid was removed by filtration, hexane was added, the supernatant was removed, and the solvent was removed under reduced pressure to obtain 37.7 g of compound 55 (yield 109%).

[0629] Compound 56 was synthesized using compound 51.

[0630]

[0631] Magnesium (12.37 g), THF (360 mL), and iodine (two grains) were added to an argon-purged flask and stirred. After the purple color of the iodine disappeared, a solution containing 1-bromo-3,5-diphenylbenzene (148.48 g) and THF (280 mL) was added dropwise to generate a Grignard reagent. A THF (820 mL) solution of compound 51 (35.88 g), synthesized by the method described in WO 2011 / 136311, was added dropwise so that the internal temperature did not exceed 40°C, yielding a reaction solution. The mixture was then stirred overnight, and a 10% aqueous ammonium chloride solution (450 mL) was poured into the reaction solution to terminate the reaction, followed by separation. The organic layer was dehydrated over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated using a rotary evaporator. The residue was purified by silica gel column chromatography (using hexane and ethyl acetate as the developing solvent) to obtain 128.6 g of Compound 56 (yield: 99%).

[0632] Compound 57 was synthesized using compound 56.

[0633]

[0634] Compound 56 (128.6 g) and toluene (1376 mL) were placed in an argon-purged flask, and the inside of the reaction vessel was purged with nitrogen. Then, p-toluenesulfonic acid monohydrate (5.39 g) was added and heated to 100°C. After stirring for 1.5 hours, the mixture was cooled to room temperature to obtain a reaction solution. The reaction solution was washed with water, and the organic layer was dehydrated with magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was concentrated using a rotary evaporator. Hexane (150 mL) was added to precipitate a solid, and then toluene (50 mL) and hexane (50 mL) were added. The mixture was ice-cooled for 60 minutes, and the precipitated solid was filtered and dried to obtain 106 g of compound 57 (yield 96%).

[0635] Compound 57 was used to synthesize compound 58.

[0636]

[0637] Compound 57 (28.38 g), tetraethylethylenediamine (6.5 mL), and 568 mL of anhydrous THF were placed in an argon-purged flask and stirred to dissolve. The solution was then cooled to -65°C in a cooling bath containing dry ice and acetone, after which a 1.6 mol / L nBuLi hexane solution (69.9 mL) was added dropwise and stirred at -65°C for 1 hour. While maintaining the temperature at -65°C, a solution of triisopropoxyborane (22.96 g) dissolved in 11.4 mL of THF was added dropwise, and the mixture was stirred at -65°C for an additional 1 hour, after which the temperature was raised to room temperature. Next, 329 mL of 10% hydrochloric acid was added to the reaction solution, and the mixture was separated. Magnesium sulfate and trimethylolethane (15.72 g) were added to the organic layer, and the mixture was stirred at room temperature for 1 hour. The magnesium sulfate was removed by filtration. The filtrate was evaporated under reduced pressure to remove the solvent, and chloroform (480 mL) was added. The mixture was refrigerated overnight, and the precipitated solid was removed. The filtrate was evaporated under reduced pressure to obtain a crude product, which was recrystallized from ethanol and hexane to obtain 36.18 g (yield 91.5%) of compound 58.

[0638] Compound 59 was synthesized according to the procedure described in the literature (Japanese Patent No. 6070722).

[0639]

[0640] Compound 55 (0.39 mmol), compound 58 (0.39 mmol), compound 59 (1.18 mmol), 4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole (0.40 mmol), 4,7-dibromo[1,2,5]thiadiazolo[3,4-c]pyridine (1.60 mmol), water (59.5 g), a 40% by mass aqueous potassium phosphate solution (10.5 mL), THF (42 mL), tetralin (20 mL), and bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol) were added as raw materials to a glass reaction vessel equipped with a cooling device at room temperature, and the mixture was stirred at 65 ° C. for 1 hour. A mixed solution of phenylboric acid (2 mmol) and a 40% by mass aqueous potassium phosphate solution (7.2 mL) was added as raw materials to the reaction vessel, and the mixture was stirred at 65 ° C. for 1 hour. The resulting organic layer was washed with an aqueous solution of sodium diethyldithiocarbamate, aqueous acetic acid, and water, and then the washed organic layer was added to methanol and the precipitated solid was collected by filtration as a crude polymer. The resulting crude polymer was dissolved in tetralin and passed through 5B (JIS P 3801: 5 type B) filter paper, and then added to methanol again and the precipitated solid was collected by filtration to obtain polymer compound P-21.

[0641] <Ink Preparation> [Preparation of Ink (I-1)] The following components were mixed and stirred at 60°C for 8 hours. 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% by mass Solvent: chloroform / 1-chloronaphthalene = 97 wt% / 3 wt%...the balance to make the total ink 100% by mass

[0642] C60PCBM ([6,6]-Phenyl C61 butylic acid methyl ester) was commercially available under the trade name "E100" manufactured by Frontier Carbon Corporation and used.

[0643] [Preparation of Inks (I-2) to (I-3)] Ink (I-2) or ink (I-3) was obtained in the same manner as in the preparation of ink (I-1), except that compound N-1 was changed to compound RN-1 or compound RN-2.

[0644] [Preparation of Ink (I-4)] Ink (I-4) was obtained in the same manner as in the preparation of Ink (I-1), except that polymer compound P-19 was changed to polymer compound P-20.

[0645] [Preparation of Inks (I-5) to (I-7)] Inks (I-5) to (I-7) were obtained in the same manner as in the preparation of Ink (I-1), except that Compound N-1 was changed to Compounds N-2 to N-4.

[0646] [Preparation of Ink (I-8)] The following components were mixed and stirred at 60°C for 8 hours. The resulting mixture was filtered using a filter to obtain Ink (I-8). P-type semiconductor material: polymer compound P-2...2.4% by mass N-type semiconductor material: compound N-5...1.7% by mass Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90 wt% / 1 wt%...the balance to make the total ink 100% by mass

[0647] [Preparation of Ink (I-9)] The following components were mixed and stirred at 60°C for 8 hours. The resulting mixture was filtered using a filter to obtain Ink (I-9). P-type semiconductor material: polymer compound P-21...2.3% by mass N-type semiconductor material: compound N-6...2.3% by mass Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90 wt% / 1 wt%...the balance to make the total ink 100% by mass

[0648] [Preparation of Ink (I-10)] The following components were mixed and stirred at 60°C for 8 hours. The resulting mixture was filtered using a filter to obtain Ink (I-10). P-type semiconductor material: polymer compound P-2...2.3% by mass N-type semiconductor material: compound N-7...2.3% by mass Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90 wt% / 1 wt%...the balance to make the total ink 100% by mass

[0649] [Preparation of Ink (I-11)] Ink (I-11) was obtained in the same manner as in the preparation of Ink (I-10), except that Compound N-7 was changed to Compound N-8.

[0650] [Preparation of Ink (I-12) to Ink (I-14)] Inks (I-12) to (I-14) were obtained in the same manner as in the preparation of Ink (I-9), except that Compound N-6 was changed to Compounds N-9 to N-11.

[0651] [Preparation of Ink (I-15)] Ink (I-15) was obtained in the same manner as in the preparation of Ink (I-14), except that Compound P-21 was changed to Compound P-1.

[0652] Example 1 [Production of Photoelectric Conversion Element and Sealed Body Thereof] 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.

[0653] Next, the zinc oxide dispersion was applied to the cleaned glass substrate by spin coating to form a coating film, and then the substrate was placed on a hot plate and dried in the atmosphere at 120°C for 10 minutes to form the coating film as an electron transport layer.

[0654] Next, ink (I-1) was applied onto the electron transport layer by spin coating to form a coating film, which was then dried by heating for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heated for 10 minutes at 100°C on a hot plate in a nitrogen atmosphere (post-bake step) to form an active layer. The thickness of the formed active layer was approximately 350 nm.

[0655] Next, molybdenum oxide (MoO ３ A ) layer was formed to a thickness of about 30 nm to serve as a hole transport layer.

[0656] 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.

[0657] 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.

[0658] [Evaluation of Photoelectric Conversion Element (Dark Current)] For the manufactured Sample 1, a voltage of −10 V to 2 V was applied to the sealed body of the photodetector element in a dark state where no light was irradiated, and the current value when a reverse bias voltage of −3 V was applied, measured using a known method, was obtained as the dark current value. The results are shown in Table 1 below.

[0659] Examples 2 to 12, Comparative Examples 1 and 2 Sealed photoelectric conversion elements were produced and evaluated using inks (I-2) to (I-14) instead of ink (I-1) in the same manner as in Example 1. The results are shown in Table 1 below.

[0660]

[0661] As shown in Table 1, the photoelectric conversion element using the compound of the present disclosure as the n-type semiconductor material was able to reduce the dark current value to about 1 / 100 to 1 / 2 compared to a photoelectric conversion element using a conventional n-type semiconductor material.

[0662] [Evaluation of Photodetector Element] A reverse bias voltage of −3 V was applied to the sealed body of the manufactured photodetector element, and the external quantum efficiency (EQE) and dark current at this applied voltage were measured and evaluated using a solar simulator (CEP-2000, manufactured by Bunkoukeiki Co., Ltd.) and a source meter (KEITHLEY 2450 Source Meter, manufactured by Keithley Instruments, Inc.).

[0663] Regarding the EQE, first, a reverse bias voltage of −3 V was applied to the sealed body of the photodetector, and the current value generated when irradiated with light of 1300 nm was measured, and the EQE value at a wavelength of 1300 nm was calculated using a known method.

[0664] Next, the specific detectivity (D*) (Jones) at an applied voltage of −3 V was calculated using the obtained measured values ​​and the calculation formula shown below.

[0665] (Number 1) D ＊ =(λ / 1240)×(EQE) / (2eJd) ０．５

[0666] In the above formula, EQE is the external quantum efficiency, which represents the EQE at the wavelength λ, and Jd represents the dark current.

[0667]

[0668] In Table 2, N-6 and N-11 have acceptors containing a quinoxaline skeleton.

[0669] As shown in Table 2, a photoelectric conversion element manufactured using a composition employing an n-type semiconductor material having a predetermined acceptor group, which is a compound of the present disclosure, and employing a polymer compound containing at least one selected from the group consisting of a structural unit represented by the above-mentioned formula (3) and a structural unit represented by the above-mentioned formula (4), not only reduced dark current as shown in Table 1, but also exhibited high D ＊ A device exhibiting the following was obtained.

[0670] REFERENCE SIGNS LIST 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): (In formula (1), D is each independently a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds; L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds; L2 does not have the same chemical structure as D and is an aromatic group having two bonds; n is 1 or 2, m is 0 or 1, and n+m=2; and A1 and A2 are acceptor groups.) 2. The compound according to claim 1, which is represented by the following formula (2): (In formula (2), D is a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds; L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds; L2 does not have the same chemical structure as D and is an aromatic group having two bonds; and A1 and A2 are acceptor groups.) 3. The compound according to claim 1 or 2, wherein the polycyclic aromatic group comprises a five-membered ring structure, and the two bonds of the polycyclic aromatic group each extend from the five-membered ring structure.

4. The compound according to claim 1 or 2, wherein the conjugated structure connecting the two bonds in L2 via the shortest distance contains three or less double bonds.

5. The compound according to claim 1 or 2, wherein L1, L1' and L2 each independently have two or less double bonds in a conjugated structure connecting the two bonds in the shortest distance.

6. The compound according to claim 1 or 2, wherein in D, the polycyclic aromatic group has a side chain, the carbon to which the side chain is bonded is an sp3 carbon or an sp2 carbon, and the side chain has an aromatic ring or a branched chain.

7. The compound according to claim 1 or claim 2, wherein L1, L1' and L2 are all different chemical structures from each other, or any two of L1, L1' and L2 are the same chemical structure.

8. The compound according to claim 1 or 2, wherein D is a donor group having a side chain of 6 or more carbon atoms.

9. The compound according to claim 1 or 2, wherein D, L1, L1' and L2 all have a sulfur-containing heterocycle.

10. The compound according to claim 1 or 2, wherein D is each independently any group represented by the following formula (D-1) to (D-7): In formulas (D-1), (D-2), (D-6) and (D-7), X is any of groups represented by the following formulas (X-1) to (X-6). In formulae (D-3) to (D-7) and formulae (X-1) to (X-6), R Ｄ１ each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio 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 carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ Either one of them may not be present.) 11. The compound according to claim 1 or 2, wherein L1 and L1' are each independently any of groups represented by the following formulae (L1-1) to (L1-9). (In formulas (L1-1) to (L1-9), R Ｌ１ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, 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 carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group.

12. The compound according to claim 1 or 2, wherein L2 is each independently any of groups represented by the following formulas (L2-1) to (L2-9). (In formulas (L2-1) to (L2-9), R Ｌ２ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, 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 carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group.

13. The compound according to claim 1 or 2, wherein A1 and A2 are each independently any of groups represented by the following formulas (a-1) to (a-8): (In formula (a-1) to formula (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.

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

15. The composition according to claim 14, wherein the p-type semiconductor material is a polymeric 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): (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): In formulae (Z-1) to (Z-7), R each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, 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 carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group; In each of formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different. ５ represents a divalent aromatic heterocyclic group.

16. An ink comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the n-type semiconductor material comprises the compound according to claim 1 or claim 2.

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

18. The photoelectric conversion element according to claim 17, which is a photodetection element.

19. An optical sensor comprising the photoelectric conversion element according to claim 18.

20. A composition comprising a compound represented by the following formula (1) and a polymeric 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): (In formula (1), D's are each independently a polycyclic aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains four or more double bonds; L1 and L1' are each independently an aromatic group having two bonds, and the conjugated structure connecting the two bonds at the shortest distance contains three or less double bonds; L2 does not have the same chemical structure as D and is an aromatic group having two bonds; n is 1 or 2, m is 0 or 1, and n+m=2; and A1 and A2 are each independently an acceptor group represented by any of formulae (a-5) to (a-8) below.) (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): In formula (Z-1) to formula (Z-7), R each independently represents an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, or a cycloalkyl group which may have a substituent, and when there are two R in each of formula (Z-1) to formula (Z-7), the two R may be the same or different. In formula (4), Ar ５ represents a divalent aromatic heterocyclic group. (In formula (a-5) to formula (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.

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