Compound and photoelectric conversion element using the same

Abstract

To provide a new semiconductor material.SOLUTION: A compound represented by the following formula (I). A1-B1-A1 (I) (In (I), A1 represents an electron-attracting group, and B1 represents a divalent group containing two or more structural units that are connected by a single bond to form a π-conjugated system, and at least one of the two or more structural units is the first structural unit represented by the following formula (II), and the remaining second structural unit other than the first structural unit is a divalent group containing an unsaturated bond, an arylene group or a heteroarylene group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound and a photoelectric conversion element using the compound as a semiconductor material. [Background technology]

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

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

[0004] In recent years, there has been a demand for further improvements in the properties of photoelectric conversion elements, and therefore, various semiconductor materials have been developed and reported (see Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Chinese Patent Application Publication No. 107652304 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the n-type semiconductor material reported in Patent Document 1 is not sufficient to satisfy the characteristics required for recent photoelectric conversion elements.

[0007] Therefore, there is a demand for further semiconductor materials that can satisfy the properties required for photoelectric conversion elements. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by a compound having a specific structure described below, and have thus completed the present invention.

[0009] Therefore, the present invention provides the following [1] to

[14] . [1] A compound represented by the following formula (I): A 1 -B 1 -A 1 (I) (In formula (I), A 1 represents an electron-withdrawing group, B 1 represents a divalent group containing two or more structural units that are linked by single bonds to form a π-conjugated system, at least one of the two or more structural units is a first structural unit represented by the following formula (II), and the remaining second structural units other than the first structural units are divalent groups containing unsaturated bonds, arylene groups, or heteroarylene groups. Two As 1 may be different from each other. When there are two or more first constitutional units, the two or more first constitutional units may be the same as or different from each other. When there are two or more second constitutional units, the two or more second constitutional units may be the same as or different from each other. [ka] (In formula (II), Ar 1 and Ar 2 each independently represents an optionally substituted aromatic carbocycle or an optionally substituted aromatic heterocycle, Y represents a group represented by -C(=O)- or an oxygen atom; R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, cyano group, nitro group, -C(=O)-R a or a group represented by -SO2-R b represents a group represented by R a and R b are each independently hydrogen atoms, an alkyl group which may have a substituent, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent. Multiple R's may be the same or different. [2] B 1 The compound according to [1], which contains two or more of the first constitutional units. [3] The compound according to [1] or [2], wherein the first constitutional unit is a constitutional unit represented by the following formula (III): [ka] (In formula (III), Y and R are as defined above, X 1 and X 2 each independently represents a sulfur atom or an oxygen atom, Z 1 and Z 2 each independently represents a group represented by ═C(R)— or a nitrogen atom. [4] B 1 The compound according to any one of [1] to [3], which contains three or more of the first constitutional units. [5] The compound according to any one of [1] to [4], wherein the second constitutional unit is selected from the group consisting of a divalent group containing an unsaturated bond and a group represented by the following formulas (IV-1) to (IV-9): [ka] (In formulas (IV-1) to (IV-9), X 1 , X 2 , Z 1 , Z 2 and R is as defined above. When there are two R's, the two R's may be the same or different. [6] B 1 The compound according to any one of [1] to [3], wherein the first structural unit is a divalent group in which 2 to 4 first structural units are linked together. [7] B 1is a divalent group having any one structure selected from the group consisting of structures represented by the following formulae (V-1) to (V-9): -CU1-CU2-CU1- (V-1) ―CU1-CU2-CU1-CU2―CU1― (V-2) -CU2―CU1―CU2―CU1―CU2― (V-3) ―CU1-CU2-CU1-CU2―CU1-CU2-CU1- (V-4) -CU1-CU1- (V-5) -CU2-CU1-CU2- (V-6) -CU1-CU1-CU1- (V-7) -CU2-CU1-CU1-CU2- (V-8) -CU2-CU1-CU1-CU1-CU2- (V-9) (In formulas (V-1) to (V-9), CU1 represents the first constitutional unit; CU2 represents the second constitutional unit. When there are two or more CU1s, the two or more CU1s may be the same or different from each other, and when there are two or more CU2s, the two or more CU2s may be the same or different from each other. [8] A composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises the compound according to any one of [1] to [7]. [9] An ink comprising the composition according to [8] and a solvent.

[10] 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, wherein the n-type semiconductor material comprises the compound according to any one of [1] to [7].

[11] The photoelectric conversion element according to

[10] , which is a photodetector element.

[12] An image sensor comprising the photoelectric conversion element according to

[11] .

[13] A fingerprint authentication device including the photoelectric conversion element described in

[11] .

[14] A vein authentication device including the photoelectric conversion element described in

[11] .

[0010] The compound of the present invention may also be in the following embodiment [X]. [X] The compounds according to [1] are excluded if they are compounds represented by the following formulae X-1 to X-3. [ka] [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a novel compound that can suppress a decrease in the external quantum efficiency of a photoelectric conversion element due to heat treatment in a manufacturing process of the photoelectric conversion element or in a process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, and can improve heat resistance, and a photoelectric conversion element using the same. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element. [Figure 2] FIG. 2 is a diagram illustrating a configuration example of the image detection unit. [Figure 3] FIG. 3 is a diagram illustrating a configuration example of the fingerprint detection unit. [Figure 4] FIG. 4 is a diagram schematically illustrating an example of the configuration of an image detection unit for an X-ray imaging device. [Figure 5] FIG. 5 is a diagram illustrating a configuration example of a vein detection unit for a vein authentication device. [Figure 6] FIG. 6 is a diagram showing a schematic configuration example of an image detection unit for an indirect type TOF distance measuring device. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, a compound according to an embodiment of the present invention will be described, and further, a photoelectric conversion element using the compound according to this embodiment will be described with reference to the drawings. Note that the drawings merely show the shape, size, and arrangement of the components to the extent that the invention can be understood. The present invention is not limited by the following description, and each component can be appropriately modified within the scope of the present invention. Furthermore, the configuration according to the embodiment of the present invention is not necessarily manufactured or used in the arrangement shown in the drawings.

[0014] First, terms commonly used in the following description will be explained.

[0015] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0016] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0017] "Polymer compounds" are compounds that have a molecular weight distribution and have a number average molecular weight equivalent to polystyrene of 1 x 10 3 More than 1×10 8 The term "polymer" refers to a polymer having the following structure: The total amount of structural units contained in the polymer compound is 100 mol %.

[0018] The term "structural unit" refers to a residue derived from a raw material compound (monomer), of which one or more are present in the compound of this embodiment and the polymer compound.

[0019] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0020] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0021] The embodiment of "optionally having a substituent" includes both a case where all hydrogen atoms constituting the compound or group are unsubstituted, and a case where one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0022] 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. Note that, when referring to the number of carbon atoms in this specification, the number of carbon atoms does not include the number of carbon atoms of substituents.

[0023] In this specification, unless otherwise specified, the "alkyl group" may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkyl group, not including the number of carbon atoms in substituents, is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20. The number of carbon atoms in a branched or cyclic alkyl group, not including the number of carbon atoms in substituents, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.

[0024] Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isoamyl, 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, cyclohexylmethyl, cyclohexylethyl, n-octyl, 2-ethylhexyl, 3-n-propylheptyl, adamantyl, n-decyl, 3,7-dimethyloctyl, 2-ethyloctyl, 2-n-hexyldecyl, n-dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl groups.

[0025] 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.

[0026] 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.

[0027] 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 is usually 3 to 30, and preferably 12 to 19, not including the number of carbon atoms in the substituent.

[0028] 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.

[0029] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0030] The term "p-valent aromatic carbocyclic group" refers to the atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent. The p-valent aromatic carbocyclic group may further have a substituent.

[0031] The term "aryl group" refers to a monovalent aromatic carbocyclic group, which is the atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring from an aromatic hydrocarbon which may have a substituent.

[0032] The aryl group may have a substituent. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0033] The "alkyloxy group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkyloxy group, not including the number of carbon atoms in the substituent, is usually 1 to 40, and preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkyloxy group, not including the number of carbon atoms in the substituent, is usually 3 to 40, and preferably 4 to 10.

[0034] 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.

[0035] 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 is usually 3 to 30, and preferably 12 to 19, not including the number of carbon atoms of the substituent.

[0036] 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 is substituted with a fluorine atom or an alkyl group.

[0037] The number of carbon atoms in the "aryloxy group" is usually 6 to 60, and preferably 6 to 48, not including the number of carbon atoms in the substituent.

[0038] The aryloxy group may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0039] The "alkylthio group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkylthio group, not including the number of carbon atoms in the substituent, is usually 1 to 40, and preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkylthio group, not including the number of carbon atoms in the substituent, is usually 3 to 40, and preferably 4 to 10.

[0040] 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.

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

[0042] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0043] The number of carbon atoms in the "arylthio group" is usually 6 to 60, and preferably 6 to 48, not including the number of carbon atoms in substituents.

[0044] 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.

[0045] The term "p-valent heterocyclic group" (where p represents an integer of 1 or greater) refers to the atomic group remaining after removing p hydrogen atoms from the hydrogen atoms directly bonded to carbon atoms or heteroatoms that constitute the ring of an optionally substituted heterocyclic compound.

[0046] The p-valent heterocyclic group may further have a substituent. The number of carbon atoms in the p-valent heterocyclic group is usually 2 to 30, and preferably 2 to 6, not including the number of carbon atoms in the substituent.

[0047] 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 p-valent heterocyclic group includes a "p-valent aromatic heterocyclic group."

[0048] The term "p-valent aromatic heterocyclic group" refers to the atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an aromatic heterocyclic compound which may have a substituent. The p-valent aromatic heterocyclic group may further have a substituent.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] The monovalent heterocyclic group has usually 2 to 60 carbon atoms, and preferably 4 to 20 carbon atoms, not including the number of carbon atoms of the substituent.

[0053] 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.

[0054] The term "substituted amino group" refers to an amino group having a substituent. Examples of the substituent on the amino group include an alkyl group, an aryl group, and a monovalent heterocyclic group, and an alkyl group, an aryl group, or a monovalent heterocyclic group is preferred. The number of carbon atoms in the substituted amino group is usually 2 to 30.

[0055] 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.

[0056] The "acyl group" may have a substituent. The number of carbon atoms in the acyl group, not including the number of carbon atoms in the substituent, is usually 2 to 20, and 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.

[0057] 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.

[0058] The imine residue usually has 2 to 20 carbon atoms, and preferably has 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the following structural formulas.

[0059] [ka]

[0060] 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 1 to 20, and 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.

[0061] The term "acid imide group" refers to the atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is usually 4 to 20. Specific examples of the acid imide group include groups represented by the following structural formula:

[0062] [ka]

[0063] The term "substituted oxycarbonyl group" refers to a group represented by R'-O-(C=O)-, where R' represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0064] The number of carbon atoms in the substituted oxycarbonyl group is usually 2 to 60, and preferably 2 to 48, not including the number of carbon atoms in the substituent.

[0065] 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.

[0066] The "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkenyl group, not including the number of carbon atoms in substituents, is usually 2 to 30, and preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkenyl group, not including the number of carbon atoms in substituents, is usually 3 to 30, and preferably 4 to 20.

[0067] The alkenyl group may have a substituent. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0068] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group, not including the number of carbon atoms in the substituent, is usually 3 to 30, and preferably 12 to 19.

[0069] 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.

[0070] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0071] The "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkenyl group, not including the number of carbon atoms in substituents, is usually 2 to 20, and preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkenyl group, not including the number of carbon atoms in substituents, is usually 4 to 30, and preferably 4 to 20.

[0072] The alkynyl group may have a substituent. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0073] 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 in the substituent, is usually 4 to 30, and preferably 12 to 19.

[0074] 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.

[0075] Examples of the substituted cycloalkynyl group include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0076] 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 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0077] The symbol "*" that may be added to a chemical formula represents a bond.

[0078] "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.

[0079] The ink may be a solution, or may be a dispersion such as a dispersion, emulsion, or suspension.

[0080] 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.

[0081] "External quantum efficiency" is also called EQE (External Quantum Efficiency), and refers to the ratio (%) of the number of electrons that can be extracted outside the photoelectric conversion element out of the number of electrons generated relative to the number of photons irradiated onto the photoelectric conversion element.

[0082] 1.Compound First, the compound of this embodiment will be described. The compound of this embodiment can be suitably used as a semiconductor material, particularly in the active layer of a photoelectric conversion element. Whether the compound of this embodiment functions as a p-type semiconductor material or an n-type semiconductor material in the active layer can be determined relatively from the value of the HOMO energy level or the value of the LUMO energy level of the selected compound. The compound of this embodiment can be suitably used, particularly as an n-type semiconductor material, in the active layer of a photoelectric conversion element.

[0083] The relationship between the HOMO and LUMO energy levels of the p-type semiconductor material contained in the active layer and the HOMO and LUMO energy levels of the n-type semiconductor material can be appropriately set within the range in which the photoelectric conversion element (photodetector element) operates.

[0084] The compound of this embodiment is a compound represented by the following formula (I). A 1 -B 1 -A 1 (I) In formula (I), A 1 represents an electron-withdrawing group, B 1 represents a divalent group containing two or more structural units that are linked by single bonds to form a π-conjugated system, at least one of the two or more structural units is a first structural unit represented by the following formula (II) (hereinafter also referred to as the first structural unit CU1), and the remaining second structural unit other than the first structural unit (hereinafter also referred to as the second structural unit CU2) is a divalent group containing an unsaturated bond, an arylene group, or a heteroarylene group. Two As 1 may be different from each other. When there are two or more first constitutional units, the two or more first constitutional units may be the same as or different from each other. When there are two or more second constitutional units, the two or more second constitutional units may be the same as or different from each other.

[0085] [ka]

[0086] In formula (II), Ar 1 and Ar 2 each independently represents an optionally substituted aromatic carbocycle or an optionally substituted aromatic heterocycle, Y represents a group represented by -C(=O)- or an oxygen atom; R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, cyano group, nitro group, -C(=O)-R a or a group represented by -SO2-R b represents a group represented by R a and R b are each independently hydrogen atoms, an alkyl group which may have a substituent, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent. A plurality of R's may be the same or different.

[0087] The compound of this embodiment is a non-fullerene compound represented by the above formula (I), which has two A groups which are electron-withdrawing monovalent groups. 1 is a divalent group containing two or more structural units that are linked by single bonds to form a π-conjugated system, B 1 The compound A that can constitute the compound of this embodiment is a compound in which A is bonded to both ends of the compound. 1 and B 1 This will be explained in detail.

[0088] (1)A 1 About A 1 is an electron-withdrawing monovalent group. A is an electron-withdrawing monovalent group 1 Examples of the group include a group represented by -CH=C(-CN)2 and groups represented by the following formulae (a-1) to (a-9).

[0089] [ka]

[0090] In formulas (a-1) to (a-7), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.

[0091] Examples of the carbocyclic ring represented by T which may have a substituent include aromatic carbocyclic rings, preferably aromatic carbocyclic rings. Specific examples of the carbocyclic ring represented by T which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, preferably a benzene ring, a naphthalene ring, and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0092] Examples of the heterocycle represented by T which may have a substituent include an aromatic heterocycle, preferably an aromatic carbocycle. Specific examples of the heterocycle represented by T which may have a substituent include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, more preferably a thiophene ring. These rings may have a substituent.

[0093] Examples of the substituent that the carbocyclic or heterocyclic ring represented by T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, and a monovalent heterocyclic group, and preferably a fluorine atom, a chlorine atom, an alkyloxy group having 1 to 6 carbon atoms, and / or an alkyl group having 1 to 6 carbon atoms.

[0094] X 4 , X 5 , and X 6each independently represents an oxygen atom, a sulfur atom, an alkylidene group, or a group represented by ═C(—CN) 2 , and is preferably an oxygen atom, a sulfur atom, or a group represented by ═C(—CN) 2 .

[0095] X 7 represents a hydrogen atom or a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or a monovalent heterocyclic group. 7 is preferably a cyano group.

[0096] R a1 , R a2 , R a3 , R a4 , and R a5 each independently represents a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyloxy group, an optionally substituted aryl group, or a monovalent heterocyclic group, and is preferably an optionally substituted alkyl group or an optionally substituted aryl group.

[0097] [ka]

[0098] In formula (a-8) and formula (a-9), R a6 and R a7 each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted monovalent aromatic carbocyclic group, or an optionally substituted monovalent aromatic heterocyclic group, a6 and R a7 may be the same or different from each other.

[0099] A 1Specific examples of the electron-withdrawing group represented by the formula (a-1-1) include groups represented by the following formulas (a-1-1) to (a-1-4), as well as groups represented by formulas (a-5-1), (a-6-1) and (a-7-1).

[0100] [ka]

[0101] In the formulas (a-1-1) to (a-1-4), as well as the formulas (a-5-1), (a-6-1) and (a-7-1), Multiple R's a10 each independently represents a hydrogen atom or a substituent, R a1 , R a2 , R a3 , R a4 , and R a5 are each independently as defined above.

[0102] R a10 is preferably a hydrogen atom, a halogen atom, an alkyloxy group, a cyano group, or an alkyl group. a1 , R a2 , R a3 , R a4 , and R a5 is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.

[0103] A 1 Preferred examples of the electron-withdrawing group represented by the formula include groups represented by the following formula:

[0104] [ka]

[0105] [ka]

[0106] (2)B 1 About B 1 is a divalent group containing two or more structural units that are linked by single bonds to form a π-conjugated system. 1 contains one or more pairs of atoms that are π-bonded to each other, and the π electron cloud is B 1 It is a divalent group that extends throughout the

[0107] B 1 At least one of the two or more structural units that can constitute the above structure is a first structural unit CU1 represented by the above formula (II), and the remaining second structural unit CU2 other than the first structural unit CU1 is a divalent group containing an unsaturated bond, an arylene group, or a heteroarylene group. In the compound of this embodiment, B 1 preferably contains two or more first constitutional units CU1. The first constitutional unit CU1 and the second constitutional unit CU2 will be specifically described below.

[0108] (i) First structural unit CU1 B 1 The first structural unit CU1 that can constitute the above is a structural unit represented by the following formula (II).

[0109] [ka]

[0110] In formula (II), Ar 1 and Ar 2 and Y and R are as defined above.

[0111] Ar 1 and Ar 2 The aromatic carbocyclic rings that can constitute the above 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.

[0112] Ar 1 and Ar 2The aromatic heterocycles that can constitute the above are preferably an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a thienothiophene ring, a benzothiophene 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.

[0113] The halogen atom represented by R is preferably a fluorine atom.

[0114] The alkyl group represented by R, which may have a substituent, is preferably an alkyl group of 1 to 20 carbon atoms, which may have a substituent, more preferably an alkyl group of 1 to 15 carbon atoms, which may have a substituent, even more preferably an alkyl group of 1 to 12 carbon atoms, which may have a substituent, and even more preferably an alkyl group of 1 to 10 carbon atoms, which may have a substituent.

[0115] The substituent that the alkyl group represented by R may have is preferably a halogen atom, more preferably a fluorine atom and / or a chlorine atom.

[0116] The cycloalkyl group represented by R, which may have a substituent, is preferably a cycloalkyl group having 3 to 10 carbon atoms, which may have a substituent, more preferably a cycloalkyl group having 5 to 6 carbon atoms, which may have a substituent, and even more preferably a cyclohexyl group, which may have a substituent.

[0117] The aryl group represented by R, which may have a substituent, is preferably an aryl group having 6 to 15 carbon atoms, which may have a substituent, and more preferably a phenyl group or naphthyl group, which may have a substituent.

[0118] The substituent that the aryl group represented by R may have is preferably a halogen atom (e.g., a chlorine atom, a fluorine atom), an alkyl group having 1 to 12 carbon atoms (e.g., a methyl group, a trifluoromethyl group, a tert-butyl group, an octyl group, a dodecyl group), an alkyloxy group having 1 to 12 carbon atoms (e.g., a methoxy group, an ethoxy group, an octyloxy group), an alkylsulfonyl group having 1 to 12 carbon atoms (e.g., a dodecylsulfonyl group), and / or a cyano group.

[0119] The alkyloxy group represented by R, which may have a substituent, is preferably an alkyloxy group having 1 to 10 carbon atoms, which may have a substituent, more preferably an alkyloxy group having 1 to 8 carbon atoms, which may have a substituent, and even more preferably a methoxy group, an ethoxy group, a propyloxy group, a 3-methylbutyloxy group, or a 2-ethylhexyloxy group, and these groups may have a substituent.

[0120] The aryloxy group represented by R, which may have a substituent, is preferably an aryloxy group having 6 to 15 carbon atoms, which may have a substituent, and more preferably a phenyloxy group or an anthracenyloxy group, which may have a substituent.

[0121] The substituent that the aryloxy group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0122] The alkylthio group represented by R, which may have a substituent, is preferably an alkylthio group having 1 to 6 carbon atoms, which may have a substituent, more preferably an alkylthio group having 1 to 3 carbon atoms, which may have a substituent, and even more preferably a methylthio group or propylthio group, which may have a substituent.

[0123] The arylthio group represented by R, which may have a substituent, is preferably an arylthio group having 6 to 10 carbon atoms, which may have a substituent, and more preferably a phenylthio group, which may have a substituent.

[0124] The substituent that the arylthio group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0125] The optionally substituted monovalent heterocyclic group represented by R is preferably an optionally substituted 5- or 6-membered monovalent heterocyclic group. Examples of 5-membered monovalent heterocyclic groups include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, and pyrrolidinyl. Examples of 6-membered monovalent heterocyclic groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, piperidyl, piperazinyl, morpholinyl, and tetrahydropyranyl.

[0126] The optionally substituted monovalent heterocyclic group represented by R is more preferably a thienyl group, a furyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, or a pyrazyl group, and these groups may have a substituent.

[0127] The substituent that the monovalent heterocyclic group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms (eg, methyl group, trifluoromethyl group, propyl group, hexyl group, octyl group, dodecyl group).

[0128] The alkenyl group represented by R, which may have a substituent, is preferably an alkenyl group having 2 to 10 carbon atoms, which may have a substituent, more preferably an alkenyl group having 2 to 6 carbon atoms, which may have a substituent, and even more preferably a 2-propenyl group or a 5-hexenyl group, which may have a substituent.

[0129] The cycloalkenyl group represented by R, which may have a substituent, is preferably a cycloalkenyl group having 3 to 10 carbon atoms, which may have a substituent, more preferably a cycloalkenyl group having 6 to 7 carbon atoms, which may have a substituent, and even more preferably a cyclohexenyl group or cycloheptenyl group, which may have a substituent.

[0130] The substituent that the cycloalkenyl group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms.

[0131] The alkynyl group represented by R, which may have a substituent, is preferably an alkynyl group having 2 to 10 carbon atoms, which may have a substituent, more preferably an alkynyl group having 5 to 6 carbon atoms, which may have a substituent, and even more preferably a 5-hexynyl group or a 3-methyl-1-butynyl group, which may have a substituent.

[0132] The cycloalkynyl group represented by R, which may have a substituent, is preferably a cycloalkynyl group having 6 to 10 carbon atoms, which may have a substituent, more preferably a cycloalkynyl group having 7 to 8 carbon atoms, which may have a substituent, and even more preferably a cycloheptynyl group or cyclooctynyl group, which may have a substituent.

[0133] The substituent that the cycloalkynyl group represented by R may have is preferably a C1 to C12 alkyl group.

[0134] Each of the multiple R's is preferably an alkyl group which may have a substituent, more preferably an alkyl group of 1 to 15 carbon atoms which may have a substituent, even more preferably an alkyl group of 1 to 12 carbon atoms which may have a substituent, and even more preferably an alkyl group of 1 to 10 carbon atoms which may have a substituent. It is particularly preferred that all of the multiple R's are alkyl groups of 1 to 10 carbon atoms which may have a substituent.

[0135] -C(=O)-R represented by R a and groups represented by -SO2-R b In the group represented by a is preferably a hydrogen atom, and R b is preferably an alkyl group which may have a substituent or an alkyloxy group which may have a substituent, more preferably an alkyl group of 1 to 12 carbon atoms which may have a substituent or an alkyloxy group of 1 to 12 carbon atoms which may have a substituent, even more preferably an alkyl group of 1 to 12 carbon atoms which may have a substituent or an alkyloxy group of 1 to 6 carbon atoms which may have a substituent, and even more preferably a methyl group, ethyl group, 2-methylpropyl group, octyl group, dodecyl group, or ethoxy group, and these groups may have a substituent.

[0136] B 1 The first structural unit CU1 represented by the formula (II) that can constitute the above is preferably a structural unit represented by the following formula (III).

[0137] [ka]

[0138] In formula (III), Y and R, X 1 and X 2 , and Z 1 and Z 2 is as defined above.

[0139] B 1 The first structural unit CU1 represented by the formula (III) that can constitute the above is preferably a structural unit represented by the following formula (III-1).

[0140] [ka]

[0141] In formula (III-1), R, X1 and X 2 , and Z 1 and Z 2 is as defined above.

[0142] Examples of the constitutional unit represented by formula (III-1) include constitutional units represented by the following formulae (III-1-1) to (III-1-16).

[0143] [ka]

[0144] Preferred specific examples of the first structural unit CU1 represented by formula (III-1) include structural units represented by the following formulas.

[0145] [ka]

[0146] B 1 The first structural unit CU1 represented by formula (III) that can constitute the above is preferably a structural unit represented by the following formula (III-2).

[0147] [ka]

[0148] In formula (III-2), X 1 and X 2 , Z 1 and Z 2 and R is as defined above.

[0149] Examples of the constitutional unit represented by formula (III-2) include constitutional units represented by the following formulae (III-2-1) to (III-2-16).

[0150] [ka]

[0151] Preferred specific examples of the constitutional unit represented by formula (III-2) include constitutional units represented by the following formulas:

[0152] [ka]

[0153] In the compound of this embodiment, B 1 preferably contains three or more first constitutional units CU1.

[0154] In the compound of this embodiment, B 1 is preferably a divalent group in which at least two but no more than four first structural units CU1 are linked together.

[0155] (ii) second structural unit CU2 The second structural unit CU2 is a divalent group containing an unsaturated bond, an arylene group, or a heteroarylene group. The "divalent group containing an unsaturated bond" which is the second structural unit CU2 is, for example, a group represented by -(CR=CR)n- (where R is as defined above, and n is an integer of 1 or greater. The value of n is preferably 1 or 2, and more preferably 1), or a group represented by -C≡C-.

[0156] Specific examples of the "divalent group containing an unsaturated bond" which is the second structural unit CU2 include an ethene-1,2-diyl group, a 1,3-butadiene-1,4-diyl group, and an acetylene-1,2-diyl group.

[0157] In the compound of this embodiment, the second structural unit CU2 is preferably a structural unit selected from the group consisting of a divalent group containing an unsaturated bond and a group represented by the following formulas (IV-1) to (IV-9), and more preferably a structural unit selected from the group consisting of groups represented by the following formulas (IV-1) to (IV-6).

[0158] [ka]

[0159] In formulas (IV-1) to (IV-9), X 1 , X 2 , Z 1 , Z 2 and R is as defined above. When there are two R's, the two R's may be the same or different.

[0160] More specific preferred examples of the second structural unit CU2 include structural units represented by the following formula: These structural units may further have a substituent.

[0161] [ka]

[0162] In the compound of this embodiment, B 1 As already explained, contains two or more structural units, at least one of which is a first structural unit CU1, and the remaining structural units other than the first structural unit CU1 are second structural units CU2.

[0163] B 1 There are no particular restrictions on the combination and arrangement of the first structural unit CU1 and the second structural unit CU2 contained in the above, provided that a π-conjugated system can be formed.

[0164] B 1 is preferably a divalent group having any one structure selected from the group consisting of structures represented by the following formulae (V-1) to (V-9). -CU1-CU2-CU1- (V-1) ―CU1-CU2-CU1-CU2―CU1― (V-2) -CU2―CU1―CU2―CU1―CU2― (V-3) ―CU1-CU2-CU1-CU2―CU1-CU2-CU1- (V-4) -CU1-CU1- (V-5) -CU2-CU1-CU2- (V-6) -CU1-CU1-CU1- (V-7) -CU2-CU1-CU1-CU2- (V-8) -CU2-CU1-CU1-CU1-CU2- (V-9)

[0165] In formulas (V-1) to (V-9), CU1 represents the first constitutional unit CU1, CU2 represents the second building block CU2. When there are two or more CU1s, the two or more CU1s may be the same as or different from each other, and when there are two or more CU2s, the two or more CU2s may be the same as or different from each other.

[0166] Among the formulas (V-1) to (V-9), divalent groups having a structure represented by formula (V-1), formula (V-3), formula (V-5), formula (V-6), formula (V-7), formula (V-8) and formula (V-9) are preferred, and divalent groups having a structure represented by formula (V-1), formula (V-3), formula (V-7) and formula (V-9) are more preferred.

[0167] B 1 The total number of first structural units CU1 and second structural units CU2 that can be contained in is usually 2 or more, preferably 3 or more, and usually 7 or less, preferably 5 or less. B 1 The number of first structural units CU1 that can be contained in is usually 1 or more, preferably 2 or more, and more preferably 3 or more. B 1 The number of second structural units CU2 that can be contained in is usually 5 or less, preferably 3 or less, and more preferably 1 or less.

[0168] B 1 Specific preferred examples of include divalent groups represented by the following formulas:

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] [ka]

[0174] In the formula, R is as defined above.

[0175] Specific examples of the compound represented by formula (I) of this embodiment include compounds represented by the following formulas.

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] More specific preferred examples of the compound represented by formula (I) of this embodiment include compounds represented by the following formulae N-1 to N-16.

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] [ka]

[0186] [ka]

[0187] [ka]

[0188] The compound of this embodiment can be suitably used as a semiconductor material for the active layer of a photoelectric conversion element, particularly as a non-fullerene compound that is an n-type semiconductor material.

[0189] In particular, when the compound of this embodiment is used as an n-type semiconductor material for an active layer, it is possible to suppress a decrease in EQE due to heat treatment in a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device, and to further improve the EQE, thereby improving heat resistance.

[0190] Two or more of the compounds of this embodiment used as n-type semiconductor materials may be contained as materials for the active layer.

[0191] The active layer of a photoelectric conversion element (details will be described later) may contain only the compound of this embodiment as an n-type semiconductor material, or may contain a compound other than the compound of this embodiment, which is an n-type semiconductor material, as an additional n-type semiconductor material. The compound other than the compound of this embodiment that can be contained as an additional n-type semiconductor material may be a low molecular weight compound or a high molecular weight compound.

[0192] Examples of n-type semiconductor materials (electron-accepting compounds) other than the "compound of the present embodiment," which is a low molecular weight compound, 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.

[0193] Examples of n-type semiconductor materials other than the "compound of the present embodiment" which is a polymer compound 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.

[0194] Compounds other than the "compound of this embodiment" may include fullerene derivatives.

[0195] Here, the fullerene derivative is fullerene (C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene and C 84 It refers to a compound in which at least a part of a fullerene (C) is modified. In other words, it refers to a compound having one or more groups added to the fullerene skeleton. Hereinafter, C 60 Fullerene derivatives are called "C 60 "Fullerene derivatives" and C 70 Fullerene derivatives are called "C 70 They are sometimes called "fullerene derivatives."

[0196] There are no particular limitations on fullerene derivatives that can be used as n-type semiconductor materials other than the "compound of this embodiment" as long as they do not impair the object of the present invention.

[0197] C that can be used as an n-type semiconductor material other than the "compound of this embodiment" 60 Specific examples of fullerene derivatives include the following compounds.

[0198] [ka]

[0199] In the formula, R is as defined above. When there are multiple R, the multiple R may be the same or different.

[0200] C 70 Examples of fullerene derivatives include the following compounds:

[0201] [ka]

[0202] 2. Photoelectric conversion element The photoelectric conversion element according to this embodiment is a photoelectric conversion element including 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, wherein the n-type semiconductor material contains the compound according to this embodiment already described.

[0203] According to the photoelectric conversion element of this embodiment, 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.

[0204] Here, an example of a configuration that the photoelectric conversion element of this embodiment can take will be described. Figure 1 is a diagram schematically showing the configuration of the photoelectric conversion element of this embodiment.

[0205] 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. Hereinafter, the components that can be included in the photoelectric conversion element of this embodiment will be specifically described.

[0206] (substrate) A photoelectric conversion element is usually formed on a substrate (support substrate). It may also be sealed with a further substrate (sealing substrate). One of a pair of electrodes, consisting of an anode and a cathode, is usually formed on the substrate. The material of the substrate is not particularly limited, as long as it is a material that is not chemically changed, especially when a layer containing an organic compound is formed.

[0207] 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.

[0208] (electrode) The photoelectric conversion element includes a pair of electrodes, an anode and a cathode, at least one of which is preferably a transparent or semi-transparent electrode to allow light to enter.

[0209] Examples of transparent or semitransparent electrode materials include conductive metal oxide films and semitransparent metal thin films. Specific examples include conductive materials such as indium oxide, zinc oxide, tin oxide, and their composites, such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, as well as gold, platinum, silver, and copper. Preferred transparent or semitransparent electrode materials include ITO, IZO, and tin oxide. Alternatively, transparent conductive films made of organic compounds such as polyaniline and its derivatives, polythiophene and its derivatives, etc. may be used as electrodes. The transparent or semitransparent electrode may be an anode or a cathode.

[0210] As long as one electrode of a pair of electrodes is transparent or translucent, the other electrode may have low optical transparency. Examples of materials for electrodes with low optical transparency include metals and conductive polymers. Specific examples of materials for electrodes with low optical transparency include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, and ytterbium, alloys of two or more of these metals, alloys of one or more of these metals with one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, graphite, graphite intercalation compounds, polyaniline and its derivatives, and polythiophene and its derivatives. The alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

[0211] (active layer) The active layer provided in the photoelectric conversion element of this embodiment is assumed to have a bulk heterojunction structure, and includes a p-type semiconductor material and an n-type semiconductor material, and the n-type semiconductor material includes the compound of this embodiment (details will be described later).

[0212] In this embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness taking into consideration the balance between suppressing dark current and extracting the generated photocurrent. In particular, from the viewpoint of further reducing dark current, the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more. 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.

[0213] In this embodiment, the active layer is formed by a process including a heating treatment at a heating temperature of 200° C. or higher (details will be described later).

[0214] Here, a p-type semiconductor material that can be suitably used as the material for the active layer according to this embodiment in combination with the n-type semiconductor material, which is the compound of this embodiment already described, will be described.

[0215] The p-type semiconductor material is preferably a polymer compound having a predetermined weight average molecular weight in terms of polystyrene.

[0216] Here, the weight average molecular weight in terms of polystyrene refers to a weight average molecular weight calculated using gel permeation chromatography (GPC) and a polystyrene standard sample.

[0217] The weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in solvents.

[0218] In this embodiment, 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).Which is the donor structural unit or the acceptor structural unit can be determined relatively from the energy levels of the HOMO or LUMO.

[0219] Here, a donor building block is a building block that has an excess of π electrons, and an acceptor building block is a building block that has a deficiency of π electrons.

[0220] In this embodiment, the structural units that can constitute the p-type semiconductor material include structural units in which a donor structural unit and an acceptor structural unit are directly bonded, and also structural units in which a donor structural unit and an acceptor structural unit are bonded via any suitable spacer (group or structural unit).

[0221] 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.

[0222] The p-type semiconductor material of this embodiment is preferably a polymer compound containing a constitutional unit represented by the following formula (VI): In this embodiment, the constitutional unit represented by the following formula (VI) is usually a donor constitutional unit.

[0223] [ka]

[0224] In formula (VI), Ar 3 and Ar 4 represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents a group represented by the following formulae (Z-1) to (Z-7).

[0225] [ka]

[0226] In formulas (Z-1) to (Z-7), R is as defined above. In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] The constitutional unit represented by formula (VI) is preferably a constitutional unit represented by the following formula (VII) or (VIII): In other words, in this embodiment, the p-type semiconductor material is preferably a polymer compound containing a constitutional unit represented by the following formula (VII) or (VIII):

[0232] [ka]

[0233] In formulas (VII) and (VIII), Ar 3 , Ar 4 and R is as defined above.

[0234] Suitable examples of the structural units represented by formulas (VI) and (VIII) include structural units represented by the following formulas (VI-1) and (VI-2), and formulas (VIII-1) and (VIII-2).

[0235] [ka]

[0236] In formula (VI-1), formula (VI-2), formula (VIII-1) and formula (VIII-2), R is as defined above. When there are two R's, the two R's may be the same or different.

[0237] More specific examples of preferred structural units represented by formula (VI-1) include structural units represented by the following formulae (VI-1-1) and (VI-1-2).

[0238] [ka]

[0239] Furthermore, the constitutional unit represented by formula (VII) is preferably a constitutional unit represented by the following formula (IX): In other words, in this embodiment, the p-type semiconductor material may be a polymer compound containing a constitutional unit represented by the following formula (IX):

[0240] [ka]

[0241] In formula (IX), X 1 and X 2 are each independently a sulfur atom or an oxygen atom, Z 1 and Z 2 are each independently a group represented by ═C(R)— or a nitrogen atom, R is as defined above.

[0242] Preferred examples of the structural unit represented by formula (IX) include structural units represented by the following formulae (IX-1) to (IX-16).

[0243] [ka]

[0244] The structural unit represented by formula (IX) is X 1 and X 2 is a sulfur atom, and Z 1 and Z 2 is a group represented by ═C(R)—.

[0245] In this embodiment, the polymer compound that is the p-type semiconductor material preferably contains a constitutional unit represented by the following formula (X): In this embodiment, the constitutional unit represented by the following formula (X) is usually an acceptor constitutional unit.

[0246] [ka]

[0247] In formula (X), Ar 5 represents a divalent aromatic heterocyclic group.

[0248] Ar 5 The divalent aromatic heterocyclic group represented by the following formula (I) typically has 2 to 60 carbon atoms, preferably 4 to 60 carbon atoms, and more preferably 4 to 20 carbon atoms.

[0249] Ar 5 The divalent aromatic heterocyclic group represented by the formula (Ar) may have a substituent. 5Examples of the substituent that the divalent aromatic heterocyclic group represented by the formula (I) may have include a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amide group, an optionally substituted acid imide group, an optionally substituted substituted oxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a cyano group, and a nitro group.

[0250] As the constitutional unit represented by formula (X), constitutional units represented by the following formulae (X-1) to (X-10) are preferred.

[0251] [ka]

[0252] In formulas (X-1) to (X-10), X 1 , X 2 , Z 1 , Z 2 and R is as defined above. When there are two R's, the two R's may be the same or different.

[0253] From the viewpoint of availability of raw material compounds, X in formulas (X-1) to (X-10) 1 and X 2 are preferably sulfur atoms.

[0254] As described above, the structural units represented by formulae (X-1) to (X-10) can generally function as acceptor structural units. However, without being limited thereto, the structural units represented by formulae (X-4), (X-5) and (X-7) in particular can also function as donor structural units.

[0255] In this embodiment, 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.

[0256] Ar 5 Specific examples of the divalent aromatic heterocyclic group represented by the formula (1) include groups represented by the following formulas (101) to (191). These groups may further have a substituent.

[0257] [ka]

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] In the formulae (101) to (191), R has the same meaning as defined above. When there are multiple R, the multiple R may be the same or different.

[0262] The polymer compound that is the p-type semiconductor material of this embodiment is preferably a π-conjugated polymer compound that includes a constitutional unit represented by formula (VI) as a donor constitutional unit and a constitutional unit represented by formula (X) as an acceptor constitutional unit.

[0263] The polymer compound that is a p-type semiconductor material may contain two or more types of constitutional units represented by formula (VI), or may contain two or more types of constitutional units represented by formula (X).

[0264] For example, from the viewpoint of improving solubility in a solvent, the polymer compound that is the p-type semiconductor material of this embodiment may contain a constitutional unit represented by the following formula (XI).

[0265] [ka]

[0266] In formula (XI), Ar 6 represents an arylene group.

[0267] Ar 6 The arylene group represented by the formula (I) means the atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon also includes compounds having fused rings and compounds 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.

[0268] 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.

[0269] Ar 6 The number of carbon atoms of the arylene group represented by the following formula (I) is usually 6 to 60, not including the number of carbon atoms of the substituent, and preferably 6 to 20. The number of carbon atoms of the arylene group including the substituent is usually 6 to 100.

[0270] Ar 6Examples 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).

[0271] [ka]

[0272] [ka]

[0273] [ka]

[0274] [ka]

[0275] [ka]

[0276] [ka]

[0277] [ka]

[0278] [ka]

[0279] In the formula, R is as defined above. Multiple Rs may be the same or different.

[0280] The constitutional unit represented by formula (XI) is preferably a constitutional unit represented by the following formula (XII).

[0281] [ka]

[0282] In formula (XII), R is as defined above. The two Rs may be the same or different.

[0283] 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.

[0284] When a polymer compound serving as a p-type semiconductor material contains a constitutional unit represented by formula (VI) and / or a constitutional unit represented by formula (X), the total amount of the constitutional unit represented by formula (VI) and the constitutional unit represented by formula (X) is usually 20 mol % to 100 mol %, assuming the amount of all constitutional units contained in the polymer compound as 100 mol %, and is preferably 40 mol % to 100 mol %, and more preferably 50 mol % to 100 mol %, in order to improve the charge transport properties as a p-type semiconductor material.

[0285] Specific examples of the polymer compound that is the p-type semiconductor material of this embodiment include polymer compounds represented by the following formulas (P-1) to (P-17).

[0286] [ka]

[0287] [ka]

[0288] [ka]

[0289] [ka]

[0290] [ka]

[0291] [ka]

[0292] [ka]

[0293] In the formula, R is as defined above. Multiple Rs may be the same or different.

[0294] When the polymer compound exemplified above is used as a p-type semiconductor material, it is possible to suppress a decrease in EQE or further improve the EQE upon heat treatment in a manufacturing process of a photoelectric conversion element or a process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, and thus it is possible to improve the heat resistance of the photoelectric conversion element.

[0295] (middle class) As shown in FIG. 1, the photoelectric conversion element of this embodiment 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.

[0296] 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 of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonate)) (PEDOT:PSS).

[0297] As shown in Figure 1, the photoelectric conversion element preferably includes a hole transport layer between the anode and the active layer. The hole transport layer has the function of transporting holes from the active layer to the electrode.

[0298] 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.

[0299] The hole transport layer includes a hole transport material, examples of which include polythiophene and its derivatives, aromatic amine compounds, polymer compounds including structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO), and molybdenum oxide (MoO).

[0300] 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.

[0301] The photoelectric conversion element according to this embodiment preferably has a configuration in which the intermediate layer is an electron transport layer, and the substrate (support substrate), anode, hole transport layer, active layer, electron transport layer, and cathode are laminated in this order so as to be in contact with each other.

[0302] As shown in Fig. 1, the photoelectric conversion element of this embodiment 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.

[0303] The electron transport layer provided in contact with the cathode is sometimes called an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the cathode has the function of promoting the injection of electrons generated in the active layer into the cathode.

[0304] 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.

[0305] Examples of polyalkyleneimines and derivatives thereof include polymers obtained by polymerizing one or more alkyleneimines having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, in particular alkyleneimines having 2 to 4 carbon atoms, by a conventional method, as well as polymers obtained by reacting these with various compounds to chemically modify them. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

[0306] 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.

[0307] 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 metal oxide containing zinc is preferred, and zinc oxide is particularly preferred.

[0308] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0309] (Sealing member) The photoelectric conversion element of this embodiment preferably further includes a sealing member and is sealed with the sealing member to form a sealed body. Any suitable conventionally known sealing member can be used as the sealing member, and an example of the sealing member is a combination of a glass substrate (sealing substrate) and a sealing material (adhesive) such as a UV-curable resin.

[0310] 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.

[0311] The sealing layer is preferably formed from a material that has the property of blocking moisture (water vapor barrier property) or the property of blocking oxygen (oxygen barrier property). Examples of materials suitable for the sealing layer include organic materials such as trifluoropolyethylene, polytrifluorochloroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

[0312] 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.

[0313] (Photoelectric conversion element applications) The photoelectric conversion element of this embodiment can be used in applications such as a photodetector element and a solar cell. More specifically, the photoelectric conversion element of this embodiment can generate a photocurrent by irradiating light from the transparent or semitransparent electrode side while a voltage (reverse bias voltage) is applied between the electrodes, and can thus function as a photodetector (photosensor). Furthermore, by integrating a plurality of photodetectors, the element can also be used as an image sensor. Thus, the photoelectric conversion element of this embodiment can be particularly suitably used as a photodetector.

[0314] Furthermore, the photoelectric conversion element of this embodiment 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.

[0315] (Application example of photoelectric conversion element) The photoelectric conversion element according to this embodiment can be suitably applied as a photodetector element to the detectors provided in various electronic devices such as workstations, personal computers, portable information terminals, access control systems, digital cameras, and medical equipment.

[0316] The photoelectric conversion element of this embodiment 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 electronic devices.

[0317] The photoelectric conversion element of this embodiment can be suitably applied as an image detection section for a solid-state imaging device, and further to a time-of-flight (TOF) distance measurement device (TOF distance measuring device).

[0318] TOF distance measurement devices measure distance by detecting the reflected light emitted from a light source and reflected by the object using a photoelectric conversion element. Specifically, the distance to the object is calculated by detecting the time of flight (TOF) of the light emitted from the light source, reflected by the object, and returning as reflected light. TOF types include direct TOF and indirect TOF. Direct TOF directly measures the difference between the time light is emitted from the light source and the time the reflected light is received by the photoelectric conversion element. Indirect TOF measures distance by converting the change in charge accumulation, which depends on the time of flight, into a time change. The distance measurement principles used in indirect TOF to obtain the time of flight using charge accumulation include continuous wave (especially sinusoidal) modulation, which calculates the time of flight from the phase of the light emitted from the light source and the light reflected by the object, and pulse modulation.

[0319] Below, examples of the configurations of detection units to which the photoelectric conversion element of this embodiment can be suitably applied, such as an image detection unit for a solid-state imaging device and an image detection unit for an X-ray imaging device, a fingerprint detection unit and a vein detection unit for a biometric authentication device (e.g., a fingerprint authentication device or a vein authentication device), and an image detection unit for a TOF type distance measuring device (indirect TOF method), will be described with reference to the drawings.

[0320] (Image detector for solid-state imaging device) FIG. 2 is a diagram schematically illustrating an example of the configuration of an image detection unit for a solid-state imaging device.

[0321] The image detection unit 1 includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20, a photoelectric conversion element 10 according to an embodiment of the present invention provided on the interlayer insulating film 30, an interlayer wiring portion 32 provided to penetrate the interlayer insulating film 30 and electrically connect the CMOS transistor substrate 20 and the photoelectric conversion element 10, a sealing layer 40 provided to cover the photoelectric conversion element 10, and a color filter 50 provided on the sealing layer 40.

[0322] The CMOS transistor substrate 20 has any suitable conventionally known configuration in a manner according to the design.

[0323] The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and is equipped with functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions.

[0324] Examples of functional elements include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.

[0325] With such functional elements, wiring, etc., a signal readout circuit and the like are built into the CMOS transistor substrate 20.

[0326] The interlayer insulating film 30 can be made of any suitable insulating material known in the art, such as silicon oxide or insulating resin. The interlayer wiring portion 32 can be made of any suitable conductive material known in the art (wiring material), such as copper or tungsten. The interlayer wiring portion 32 can be, for example, a wiring in a hole formed simultaneously with the formation of the wiring layer, or a buried plug formed separately from the wiring layer.

[0327] The sealing layer 40 can be made of any suitable conventionally known material, provided that it can prevent or suppress the penetration of harmful substances such as oxygen and water that may cause functional deterioration of the photoelectric conversion element 10. The sealing layer 40 can have a configuration similar to that of the sealing member 17 already described.

[0328] The color filter 50 may be, for example, a primary color filter made of any suitable material known in the art and compatible with the design of the image detection unit 1. Alternatively, a complementary color filter, which can be thinner than a primary color filter, may be used as the color filter 50. Examples of complementary color filters that may be used include a combination of three types of color filters: (yellow, cyan, magenta), (yellow, cyan, transparent), (yellow, transparent, magenta), and (transparent, cyan, magenta). These filters may be arranged in any suitable manner compatible with the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.

[0329] The light received by the photoelectric conversion element 10 through the color filter 50 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of light received, and is output to the outside of the photoelectric conversion element 10 via the electrode as a received light signal, i.e., an electrical signal corresponding to the object to be imaged.

[0330] Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring section 32, read out by a signal readout circuit built into the CMOS transistor substrate 20, and subjected to signal processing by any suitable conventionally known functional section not shown, thereby generating image information based on the object to be imaged.

[0331] (Fingerprint detection section) FIG. 3 is a diagram schematically illustrating an example of the configuration of a fingerprint detection unit that is integrally configured with a display device.

[0332] The display device 2 of the mobile information terminal includes a fingerprint detection unit 100 that includes a photoelectric conversion element 10 according to an embodiment of the present invention as its main component, and a display panel unit 200 that is provided on the fingerprint detection unit 100 and displays a predetermined image.

[0333] In this configuration example, the fingerprint detection unit 100 is provided in an area that coincides with the display area 200a of the display panel unit 200. In other words, the display panel unit 200 is laminated integrally above the fingerprint detection unit 100.

[0334] When fingerprint detection is performed only in a part of the display area 200a, the fingerprint detection unit 100 may be provided so as to correspond to only that part of the area.

[0335] The fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs essential functions. The fingerprint detection unit 100 may include any suitable conventionally known components such as a protection film, a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film, all of which are not shown, in a form corresponding to a design that achieves desired characteristics. The fingerprint detection unit 100 may also employ the configuration of the image detection unit already described.

[0336] The photoelectric conversion elements 10 may be included in any manner within the display region 200a. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

[0337] As already explained, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 has electrodes (anodes or cathodes) provided in, for example, a matrix pattern.

[0338] The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal according to the amount of light received, and is output to the outside of the photoelectric conversion element 10 via the electrode as a received light signal, i.e., an electrical signal corresponding to the captured fingerprint.

[0339] In this configuration example, the display panel unit 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel. The display panel unit 200 may be configured as any suitable display panel having a conventionally known configuration, such as a liquid crystal display panel including a light source such as a backlight, instead of an organic EL display panel.

[0340] The display panel unit 200 is provided on the fingerprint detection unit 100 already described. The display panel unit 200 includes an organic electroluminescence element (organic EL element) 220 as a functional unit that performs an essential function. The display panel unit 200 may further include any suitable conventionally known member such as a substrate (support substrate 210 or sealing substrate 240) such as a glass substrate, a sealing member, a barrier film, a polarizing plate such as a circular polarizing plate, and a touch sensor panel 230 in a mode corresponding to desired characteristics.

[0341] In the configuration example described above, the organic EL element 220 is used as a light source for the pixels in the display area 200a, and is also used as a light source for capturing an image of a fingerprint in the fingerprint detection unit 100.

[0342] Here, the operation of the fingerprint detection unit 100 will be briefly explained. When fingerprint authentication is performed, the fingerprint detection unit 100 detects a fingerprint using light emitted from the organic EL element 220 of the display panel unit 200. Specifically, the light emitted from the organic EL element 220 passes through components present between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is reflected by the skin (finger surface) of a fingertip placed in contact with the surface of the display panel unit 200 within the display area 200a. At least a portion of the light reflected by the finger surface passes through components present therebetween, is received by the photoelectric conversion element 10, and is converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10. Then, image information about the fingerprint on the finger surface is constructed from the converted electrical signal.

[0343] The portable information terminal equipped with the display device 2 performs fingerprint authentication by comparing the obtained image information with pre-recorded fingerprint data for fingerprint authentication through any suitable steps known in the art.

[0344] (Image detector for X-ray imaging device) FIG. 4 is a diagram schematically illustrating an example of the configuration of an image detection unit for an X-ray imaging device.

[0345] The image detection unit 1 for an X-ray imaging device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20, a photoelectric conversion element 10 according to an embodiment of the present invention provided on the interlayer insulating film 30, an interlayer wiring portion 32 provided to penetrate the interlayer insulating film 30 and electrically connect the CMOS transistor substrate 20 and the photoelectric conversion element 10, a sealing layer 40 provided to cover the photoelectric conversion element 10, a scintillator 42 provided on the sealing layer 40, a reflective layer 44 provided to cover the scintillator 42, and a protective layer 46 provided to cover the reflective layer 44.

[0346] The CMOS transistor substrate 20 has any suitable conventionally known configuration in a manner according to the design.

[0347] The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and is equipped with functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions.

[0348] Examples of functional elements include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.

[0349] With such functional elements, wiring, etc., a signal readout circuit and the like are built into the CMOS transistor substrate 20.

[0350] The interlayer insulating film 30 can be made of any suitable insulating material known in the art, such as silicon oxide or insulating resin. The interlayer wiring portion 32 can be made of any suitable conductive material known in the art (wiring material), such as copper or tungsten. The interlayer wiring portion 32 can be, for example, a wiring in a hole formed simultaneously with the formation of the wiring layer, or a buried plug formed separately from the wiring layer.

[0351] The sealing layer 40 can be made of any suitable conventionally known material, provided that it can prevent or suppress the penetration of harmful substances such as oxygen and water that may cause functional deterioration of the photoelectric conversion element 10. The sealing layer 40 can have a configuration similar to that of the sealing member 17 already described.

[0352] Scintillator 42 can be made of any suitable conventional material that is known in accordance with the design of image detection unit 1 for an X-ray imaging device. Suitable examples of materials for scintillator 42 include inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadolinium oxysulfide), and GSO (gadolinium silicate), organic crystals of organic materials such as anthracene, naphthalene, and stilbene, organic liquids in which organic materials such as diphenyloxazole (PPO) and terphenyl (TP) are dissolved in organic solvents such as toluene, xylene, and dioxane, gases such as xenon and helium, and plastics.

[0353] The above components can be arranged in any suitable manner corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that the scintillator 42 can convert incident X-rays into light having a wavelength centered in the visible region and generate image data.

[0354] The reflective layer 44 reflects the light converted by the scintillator 42. The reflective layer 44 can reduce the loss of the converted light and increase the detection sensitivity. The reflective layer 44 can also block light that directly enters from the outside.

[0355] The protective layer 46 can be made of any suitable material known in the art, provided that it can prevent or suppress the penetration of harmful substances such as oxygen and water that may cause functional degradation of the scintillator 42.

[0356] Here, the operation of the image detection unit 1 for the X-ray imaging device having the above configuration will be briefly described. When radiation energy such as X-rays or gamma rays is incident on the scintillator 42, the scintillator 42 absorbs the radiation energy and converts it into light (fluorescence) with wavelengths in the ultraviolet to infrared range centered on the visible range. The light converted by the scintillator 42 is then received by the photoelectric conversion element 10. In this way, the light received by the photoelectric conversion element 10 via the scintillator 42 is converted by the photoelectric conversion element 10 into an electrical signal according to the amount of received light, and is output via the electrode to the outside of the photoelectric conversion element 10 as a received light signal, i.e., an electrical signal corresponding to the object to be imaged. The radiation energy (X-rays) to be detected may be incident from either the scintillator 42 side or the photoelectric conversion element 10 side.

[0357] Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring section 32, read out by a signal readout circuit built into the CMOS transistor substrate 20, and subjected to signal processing by any suitable conventionally known functional section not shown, thereby generating image information based on the object to be imaged.

[0358] (Vein detection unit) FIG. 5 is a diagram illustrating a configuration example of a vein detection unit for a vein authentication device. The vein detection unit 300 for the vein authentication device is composed of a cover unit 306 that defines an insertion unit 310 into which a finger to be measured (e.g., the fingertip of one or more fingers, the finger, and the palm) is inserted during measurement, a light source unit 304 that is provided in the cover unit 306 and that irradiates light onto the measurement object, a photoelectric conversion element 10 that receives the light irradiated from the light source unit 304 through the measurement object, a support substrate 11 that supports the photoelectric conversion element 10, and a glass substrate 302 that is arranged opposite the support substrate 11 with the photoelectric conversion element 10 in between, is spaced a predetermined distance from the cover unit 306, and defines the insertion unit 306 together with the cover unit 306.

[0359] In this configuration example, the light source unit 304 is a transmission type imaging method in which the light source unit 304 is integrally configured with the cover unit 306 so that the photoelectric conversion element 10 is spaced apart from the object to be measured when in use, but the light source unit 304 does not necessarily have to be positioned on the cover unit 306 side.

[0360] Provided that the light from the light source unit 304 can be efficiently irradiated onto the measurement object, for example, a reflection type imaging method in which the measurement object is irradiated from the photoelectric conversion element 10 side may be used.

[0361] The vein detection unit 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs essential functions. The vein detection unit 300 may include any suitable conventionally known components, such as a protection film, a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light blocking film, and a finger placement guide, all of which are not shown, in a form corresponding to a design that achieves desired characteristics. The vein detection unit 300 may also employ the configuration of the image detection unit 1 already described.

[0362] The photoelectric conversion elements 10 may be included in any manner. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

[0363] As already explained, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 has electrodes (anodes or cathodes) provided in, for example, a matrix pattern.

[0364] The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of received light, and is output to the outside of the photoelectric conversion element 10 via the electrode as a received light signal, i.e., an electrical signal corresponding to the imaged vein.

[0365] During vein detection (in use), the measurement object may or may not be in contact with the glass substrate 302 on the photoelectric conversion element 10 side.

[0366] Here, the operation of the vein detection unit 300 will be briefly described. During vein detection, the vein detection unit 300 detects the vein pattern of the measurement object using light emitted from the light source unit 304. Specifically, the light emitted from the light source unit 304 passes through the measurement object and is converted into an electrical signal according to the amount of light received by the photoelectric conversion element 10. Then, image information of the vein pattern of the measurement object is formed from the converted electrical signal.

[0367] In the vein authentication device, vein authentication is performed by comparing the obtained image information with pre-recorded vein data for vein authentication through any suitable steps known in the art.

[0368] (Image detector for TOF distance measuring device) FIG. 6 is a diagram showing a schematic configuration example of an image detection unit for an indirect type TOF distance measuring device.

[0369] The image detection unit 400 for a TOF distance measuring device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20, a photoelectric conversion element 10 according to an embodiment of the present invention provided on the interlayer insulating film 30, two floating diffusion layers 402 spaced apart to sandwich the photoelectric conversion element 10, an insulating layer 40 provided to cover the photoelectric conversion element 10 and the floating diffusion layer 402, and two photogates 404 provided on the insulating layer 40 and spaced apart from each other. A portion of the insulating layer 40 is exposed from the gap between the two spaced-apart photogates 404, and the remaining area is shielded from light by a light-shielding portion 406. The CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected by an interlayer wiring portion 32 provided to penetrate the interlayer insulating film 30.

[0370] In this example, the insulating layer 40 may have any suitable conventionally known structure, such as a field oxide film made of silicon oxide.

[0371] Photogate 404 may be made of any suitable material known in the art, such as polysilicon.

[0372] The image detection unit 400 for a TOF distance measuring device includes the photoelectric conversion element 10 according to an embodiment of the present invention as a functional unit that performs an essential function. The image detection unit 400 for a TOF distance measuring device may include any suitable conventionally known components such as a protection film, a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film, all of which are not shown, in a form corresponding to a design that achieves desired characteristics.

[0373] Here, the operation of the image detection unit 400 for the TOF type distance measuring device will be briefly explained. Light is emitted from a light source, reflected from the object to be measured, and the reflected light is received by the photoelectric conversion element 10. Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402, and by applying pulses alternately, the signal charge generated by the photoelectric conversion element 10 is transferred to one of the two floating diffusion layers 402, and the charge is accumulated in the floating diffusion layer 402. If the light pulse arrives at a timing that equally overlaps the timing at which the two photogates 404 are opened, the amount of charge accumulated in the two floating diffusion layers 402 will be equal. If the light pulse arrives at one photogate 404 with a delay from the time the light pulse arrives at the other photogate 404, a difference will occur in the amount of charge accumulated in the two floating diffusion layers 402.

[0374] The difference in the amount of charge accumulated in the floating diffusion layer 402 depends on the delay time of the optical pulse. The distance L to the measurement target is expressed as L = (1 / 2)ctd, where td is the round-trip time of light and c is the speed of light. Therefore, if the delay time can be estimated from the difference in the amount of charge in the two floating diffusion layers 402, the distance to the measurement target can be calculated.

[0375] The amount of light received by the photoelectric conversion element 10 is converted into an electrical signal as the difference between the amounts of charge accumulated in the two floating diffusion layers 402, and is output to the outside of the photoelectric conversion element 10 as a received light signal, i.e., an electrical signal corresponding to the object to be measured.

[0376] Next, the light receiving signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring section 32, read out by a signal readout circuit built into the CMOS transistor substrate 20, and processed by any suitable conventional functional section not shown in the figure to generate distance information based on the object to be measured.

[0377] In a process of incorporating the photoelectric conversion element of this embodiment into a device according to the above application example, a heat treatment such as a reflow process may be performed for mounting on a wiring board, etc. For example, in manufacturing an image sensor, a process including a treatment of heating the photoelectric conversion element at a heating temperature of 200° C. or higher for about 50 minutes may be performed.

[0378] According to the photoelectric conversion element of this embodiment, the compound of this embodiment (a non-fullerene compound that is an n-type semiconductor material) already described and the p-type semiconductor material already described are used as materials for the active layer. As a result, even if a heating process at a heating temperature of 200°C or higher is performed in the process of forming the active layer (details will be described later), in the process of manufacturing the photoelectric conversion element after the active layer is formed, or in the process of incorporating the manufactured photoelectric conversion element into an image sensor or a biometric authentication device, it is possible to suppress a decrease in EQE or further improve the EQE, and it is possible to effectively improve heat resistance.

[0379] Specifically, the EQE is a standardized value obtained by dividing the EQE value of a photoelectric conversion element in which the heating temperature in the pre-bake step in the active layer formation step of the photoelectric conversion element manufacturing method is 100°C by the EQE value of a photoelectric conversion element in which the heating temperature in the post-bake step is changed to a higher temperature (hereinafter referred to as "EQE"). heat / EQE 100℃ ") is preferably 0.80 or more, more preferably 0.85 or more, and even more preferably 1.0 or more.

[0380] 2. Photoelectric conversion element manufacturing method The method for manufacturing the photoelectric conversion element of this embodiment is not particularly limited. The photoelectric conversion element of this embodiment can be manufactured by combining a suitable forming method with the materials selected for forming the components.

[0381] The method for manufacturing a photoelectric conversion element of this embodiment may include a step including a heating treatment at a heating temperature of 200° C. or higher. More specifically, the active layer may be formed by a step including a heating treatment at a heating temperature of 200° C. or higher, and / or may include a step including a heating treatment at a heating temperature of 200° C. or higher after the step of forming the active layer.

[0382] Hereinafter, as an embodiment of the present invention, 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 each other in this order will be described.

[0383] (Process of preparing the substrate) In this step, for example, a support substrate provided with an anode is prepared. Alternatively, a substrate provided with a conductive thin film formed from the electrode material already described 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.

[0384] In the method for producing a photoelectric conversion element according to this embodiment, the method for forming the anode on the supporting substrate is not particularly limited. The anode can be formed on the structure where the anode is to be formed (e.g., the supporting substrate, the active layer, the hole transport layer) by any suitable conventional method such as vacuum deposition, sputtering, ion plating, plating, or coating using the materials already described.

[0385] (Hole transport layer forming step) The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the anode.

[0386] 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.

[0387] (Active layer formation process) In the method for manufacturing a photoelectric conversion element according to this embodiment, an active layer is formed on a hole transport layer. The active layer, which is a main component, can be formed by any suitable conventionally known formation process. In this embodiment, the active layer is preferably manufactured by a coating method using ink (coating liquid).

[0388] Hereinafter, the steps (i) and (ii) included in the process of forming the active layer, which is the main component of the photoelectric conversion element of the present invention, will be described.

[0389] Process (i) Any suitable coating method can be used as a method for applying the ink to a coating target, and examples of the coating method include slit coating, knife coating, spin coating, microgravure coating, gravure coating, bar coating, inkjet printing, nozzle coating, and capillary coating, more preferably slit coating, spin coating, capillary coating, and bar coating, and even more preferably slit coating or spin coating.

[0390] The ink used in the method for manufacturing a photoelectric conversion element of this embodiment includes a p-type semiconductor material and an n-type semiconductor material, and the ink includes a composition containing the compound of this embodiment as already described as the n-type semiconductor material, and a solvent.

[0391] The ink for forming an active layer of this embodiment will be described. Note that the ink for forming an active layer of this embodiment is an ink for forming a bulk heterojunction type active layer. Therefore, the ink for forming an active layer includes a composition containing the compound of this embodiment as already described as the p-type semiconductor material and the n-type semiconductor material. The ink for forming an active layer of this embodiment includes this composition and one or more solvents.

[0392] According to the ink for forming an active layer of the present embodiment, by containing a p-type semiconductor material and the "compound of the present embodiment," it is possible to suppress a decrease in EQE or to further improve the EQE due to heat treatment during, for example, the manufacturing process of a photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device, and thus it is possible to improve heat resistance.

[0393] The ink for forming the active layer according to this embodiment is not particularly limited, provided that it can form an active layer. For example, a mixed solvent of a first solvent and a second solvent, which will be described later, can be used as the solvent. Specifically, when the ink for forming the active layer 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. However, only the first solvent may be used.

[0394] The first solvent and second solvent that can be suitably used in the ink for forming the active layer of this embodiment, and their combinations, will be described below.

[0395] (1) First solvent The first solvent is preferably a solvent that can dissolve the p-type semiconductor material. The first solvent in this embodiment is an aromatic hydrocarbon.

[0396] Examples of aromatic hydrocarbons that are the first solvent include toluene, xylenes (e.g., o-xylene, m-xylene, p-xylene), o-dichlorobenzene, trimethylbenzenes (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzenes (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalenes (e.g., 1-methylnaphthalene), tetralin, and indane.

[0397] The first solvent may be composed of one type of aromatic hydrocarbon or two or more types of aromatic hydrocarbons, but is preferably composed of one type of aromatic hydrocarbon.

[0398] The first solvent is preferably one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-dichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, and indan, and more preferably toluene, o-xylene, m-xylene, p-xylene, o-dichlorobenzene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, or indan.

[0399] (2) Second solvent The second solvent is selected from the viewpoint of facilitating the production process and further improving the properties of the photoelectric conversion element. Examples of the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone, and ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate, and benzyl benzoate.

[0400] As the second solvent, for example, from the viewpoint of further reducing dark current, it is preferable to use acetophenone, propiophenone, or butyl benzoate.

[0401] (3) Combination of the first solvent and the second solvent Examples of suitable combinations of the first and second solvents include combinations of tetralin and ethyl benzoate, tetralin and propyl benzoate, and tetralin and butyl benzoate, and more preferably a combination of tetralin and butyl benzoate.

[0402] (4) Weight ratio of the first solvent to the second solvent The weight ratio of the first solvent, which is the main solvent, to the second solvent, which is the additive solvent (first solvent:second solvent), is preferably in the range of 85:15 to 99:1, from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material.

[0403] (5) Any other solvent The solvent may contain any other solvent in addition to the first and second solvents. When the total weight of all solvents contained in the ink is taken as 100% by weight, the content of the other solvent is preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 1% by weight or less. The other solvent is preferably a solvent with a boiling point higher than that of the second solvent.

[0404] (6) Optional ingredients 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 invention are not impaired.

[0405] (7) Concentration of p-type and n-type semiconductor materials The concentrations of the p-type semiconductor material and n-type semiconductor material in the ink (composition) can be set to any suitable concentration within a range that does not impair the object of the present invention, taking into consideration factors such as solubility in the solvent.

[0406] The weight ratio of the "p-type semiconductor material" to the "n-type semiconductor material" (polymer / non-fullerene compound) in the ink (composition) is usually in the range of 1 / 0.1 to 1 / 10, preferably in the range of 1 / 0.5 to 1 / 2, and more preferably 1 / 1.5.

[0407] The total concentration of the "p-type semiconductor material" and "n-type semiconductor material" in the ink is usually 0.01% by weight or more, more preferably 0.02% by weight or more, and even more preferably 0.25% by weight or more. The total concentration of the "p-type semiconductor material" and "n-type semiconductor material" in the ink is usually 20% by weight or less, preferably 10% by weight or less, and more preferably 7.50% by weight or less.

[0408] The concentration of the "p-type semiconductor material" in the ink is usually 0.01% by weight or more, more preferably 0.02% by weight or more, and even more preferably 0.10% by weight or more. The concentration of the "p-type semiconductor material" in the ink is usually 10% by weight or less, more preferably 5.00% by weight or less, and even more preferably 3.00% by weight or less.

[0409] The concentration of the "n-type semiconductor material" in the ink is usually 0.01% by weight or more, more preferably 0.02% by weight or more, and even more preferably 0.15% by weight or more. The concentration of the "n-type semiconductor material" in the ink is usually 10% by weight or less, more preferably 5% by weight or less, and even more preferably 4.50% by weight or less.

[0410] (8) Preparation of ink The ink can be prepared by a known method, for example, by mixing a first solvent or a first solvent and a second solvent to prepare a mixed solvent, and then adding a p-type semiconductor material and an n-type semiconductor material to the resulting mixed solvent, or by adding a p-type semiconductor material to the first solvent, adding an n-type semiconductor material to the second solvent, and then mixing the first solvent and the second solvent to which each material has been added.

[0411] The first and second solvents and the p-type and n-type semiconductor materials may be mixed by heating to a temperature equal to or lower than the boiling point of the solvent.

[0412] After mixing the first and second solvents with the p-type and n-type semiconductor materials, the resulting mixture may be filtered using a filter, and the resulting filtrate may be used as a filtrate. The filter may be, for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE).

[0413] The ink for forming an active layer is applied to a target selected depending on the photoelectric conversion element and its manufacturing method. The ink for forming an active layer can be applied to a functional layer of the photoelectric conversion element, in which an active layer may be present, during the manufacturing process of the photoelectric conversion element. Therefore, the target to which the ink for forming an active layer is applied varies depending on the layer structure of the photoelectric conversion element to be manufactured and the order of layer formation. For example, if the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are stacked, and the layer listed on the left is formed first, the target to which the ink for forming an active layer is applied will be the hole transport layer. Furthermore, for example, if the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are stacked, and the layer listed on the left is formed first, the target to which the ink for forming an active layer is applied will be the electron transport layer.

[0414] Process (ii) Any suitable method can be used to remove the solvent from the ink coating, i.e., to remove the solvent from the coating and solidify it. Examples of the method for removing the solvent include a method of directly heating using a hot plate in an inert gas atmosphere such as nitrogen gas, and drying methods such as hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

[0415] In the method for producing a photoelectric conversion element of this embodiment, step (ii) is a step for volatilizing and removing the solvent, and is also called a pre-baking step (first heat treatment step).

[0416] The conditions for carrying out the pre-baking and post-baking steps, i.e., the heating temperature, heating time, etc., can be set arbitrarily and suitably in consideration of the composition of the ink used, the boiling point of the solvent, and the like.

[0417] In the method for manufacturing a photoelectric conversion element of this embodiment, specifically, for example, a pre-bake step and a post-bake step can be performed using a hot plate in a nitrogen gas atmosphere.

[0418] The heating temperature in the pre-baking step is usually about 100°C. However, in the method for producing a photoelectric conversion element of this embodiment, the active layer material contains the p-type semiconductor material already described and the compound of this embodiment already described as an n-type semiconductor material, and as a result, the heating temperature in the pre-baking step and / or post-baking step can be further increased. Specifically, the heating temperature in the pre-baking step and / or post-baking step can be preferably 200°C or higher, and further 220°C or higher. The upper limit of the heating temperature is preferably 280°C or lower, and more preferably 250°C or lower.

[0419] The total heat treatment time in the pre-bake step and post-bake step can be, for example, 1 hour.

[0420] The heating temperature in the pre-baking step and the heating temperature in the post-baking step may be the same or different.

[0421] The heat treatment time can be, for example, 10 minutes or more. There is no particular upper limit to the heat treatment time, but it can be, for example, 4 hours, taking into account the takt time and the like.

[0422] The thickness of the active layer can be adjusted to any desired thickness by appropriately adjusting the solid concentration in the coating solution and the conditions in the above step (i) and / or step (ii).

[0423] The step of forming the active layer may include other steps in addition to the steps (i) and (ii) as long as the steps do not impair the object and effect of the present invention.

[0424] The method for producing a photoelectric conversion element of this embodiment 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.

[0425] (Electron transport layer forming step) The method for manufacturing a photoelectric conversion element of this embodiment includes a step of forming an electron transport layer (electron injection layer) provided on an active layer.

[0426] 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.

[0427] (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-mentioned 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 this embodiment is manufactured by the above-mentioned steps.

[0428] (Sealing body forming process) In forming the sealed body, in this embodiment, any suitable sealing material (adhesive) and substrate (sealing substrate) known in the art are used. Specifically, a sealing material such as a UV-curable resin is applied to a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the support substrate and the sealing substrate are bonded together without any gaps using the sealing material. After that, the photoelectric conversion element is sealed in the gap between the support substrate and the sealing substrate using a method suitable for the selected sealing material, such as UV light irradiation, thereby obtaining a sealed photoelectric conversion element.

[0429] 3. Manufacturing methods for image sensors and biometric authentication devices As described above, the photoelectric conversion element, particularly the photodetection element, of this embodiment can function by being incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device).

[0430] Such an image sensor and biometric authentication device can be manufactured by a manufacturing method including a process in which the photoelectric conversion element (sealed body of the photoelectric conversion element) is heated at a heating temperature of 200° C. or higher.

[0431] Specifically, when incorporating a photoelectric conversion element into an image sensor or a biometric authentication device, for example, a reflow process, which is performed when mounting the element on a wiring board, may be performed, resulting in a heating process at a temperature of 200° C. or higher, or even 220° C. or higher. However, according to the photoelectric conversion element of this embodiment, the n-type semiconductor material already described is used as the material for the active layer, and therefore the decrease in EQE of the incorporated photoelectric conversion element can be suppressed or the EQE can be further improved, and further the increase in dark current can be suppressed or the dark current can be further reduced, thereby effectively improving heat resistance, and thereby improving the characteristics of the manufactured image sensor or biometric authentication device, such as the detection accuracy.

[0432] The heat treatment time can be, for example, 10 minutes or more. There is no particular upper limit to the heat treatment time, but it can be, for example, 4 hours, taking into account the takt time and the like.

[0433] [Example] EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples described below.

[0434] In this example, the polymer compounds shown in the following Table 1 (Table 1-1 and Table 1-2) were used as p-type semiconductor materials (electron-donating compounds), and the compounds shown in the following Tables 2, 3 (Table 3-1, Table 3-2, Table 3-3 and Table 3-4) and 4 were used as n-type semiconductor materials (electron-accepting compounds).

[0435] [Table 1-1]

[0436] [Table 1-2]

[0437] [Table 2]

[0438] [Table 3-1]

[0439] [Table 3-2]

[0440] [Table 3-3]

[0441] [Table 3-4]

[0442] [Table 4]

[0443] Polymer compounds P-1 and P-2, which are p-type semiconductor materials, were synthesized with reference to the method described in WO 2011 / 052709 and used. The p-type semiconductor material P-3 was P3HT (trade name, manufactured by Sigma-Aldrich Co.) purchased from the market and used. The p-type semiconductor material P-4 was PTB7 (trade name, manufactured by 1-material Co., Ltd.) purchased from the market and used. The p-type semiconductor material P-5 was commercially available as PBDB-T-2F (product name, manufactured by 1-material Co., Ltd.). The p-type semiconductor material P-6 was PDPP3T (trade name, manufactured by Lumtec) purchased from the market and used. The p-type semiconductor material P-7 was commercially available as PDTSTPD (trade name, manufactured by 1-material Co., Ltd.).

[0444] Compounds N-1 to N-16, which are n-type semiconductor materials, were synthesized according to the synthesis examples described below and used. The compound N-17, which is an n-type semiconductor material, was obtained commercially as E100 (trade name, manufactured by Frontier Carbon Co., Ltd.) and used. The compound N-18, which is an n-type semiconductor material, was obtained commercially as COi8DFIC (trade name, manufactured by 1-material Co., Ltd.).

[0445] <Synthesis Example 1> (Synthesis of Compound 3) Compound 3 represented by the following formula was synthesized using Compound 1 and Compound 2 represented by the following formula.

[0446] [ka]

[0447] Into a 500 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 7.61 g (19.4 mmol) of compound 1, 24.8 g (40.7 mmol) of compound 2 synthesized by the method described in paragraph

[0335] of WO 2011 / 052709, and 200 mL of tetrahydronaphthalene were placed, and the flask was degassed by bubbling argon gas through it for 30 minutes.

[0448] Next, 0.88 g (0.97 mmol, 5 mol%) of Tris(dibenzylideneacetone)dipalladium(0), 1.18 g (3.88 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and 60 mL of tetrahydronaphthalene were placed in a four-neck flask and stirred for 5 minutes.

[0449] Next, 65 mL of a 3.0 M aqueous potassium phosphate solution was added to the four-neck flask, and the reaction solution was stirred while being heated in an oil bath set at 50° C. for 3 hours.

[0450] After cooling the reaction mixture, 100 mL of water and 100 mL of hexane were added to a four-necked flask, and the organic layer was separated and washed three times with water and once with a saturated aqueous sodium chloride solution.

[0451] The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was purified using a silica gel column to obtain 21.1 g (17.6 mmol, 90.8% yield) of compound 3 as an orange solid.

[0452] The NMR spectrum of the obtained compound 3 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.23 (s, 2H), 7.00 (d, J HH =4.8Hz, 2H), 6.78 (s, 2H), 6.68 (d, J HH =4.8Hz, 2H), 1.88 (m, 8H), 1.26 (br, 80H), 0.87 (t, 12H).

[0453] <Synthesis Example 2> (Synthesis of Compound 4) Compound 4 represented by the following formula was synthesized from compound 3 represented by the following formula.

[0454] [ka]

[0455] Into a 100 mL three-necked flask whose internal atmosphere had been replaced with nitrogen gas, 3.59 g (3.00 mmol) of compound 3 and 30 mL of dichloromethane were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 3.

[0456] Next, 1.17 g (9.00 mmol) of (Chloromethylene)dimethyliminium Chloride was placed in a three-necked flask, and the mixture was stirred while being heated in an oil bath set at 45° C. for 2 hours.

[0457] The reaction mixture was cooled, and then 20 mL of water was added, and the organic layer was washed twice with a saturated aqueous solution of sodium chloride. The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0458] The obtained crude product was purified by a silica gel column to obtain 3.52 g (2.81 mmol, yield 93.6%) of Compound 4 as a deep red solid.

[0459] The NMR spectrum of the obtained compound 4 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.77 (s, 2H), 7.32 (s, 2H), 7.27 (s, 2H), 6.83 (s, 2H), 1.90 (m, 8H), 1.23 (br, 80H), 0.86 (t, 12H).

[0460] Example 1 (Synthesis of Compound N-1) Compound 6 (Compound N-1) represented by the following formula was synthesized using Compound 4 and Compound 5 represented by the following formula.

[0461] [ka]

[0462] Into a 100 mL three-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 1.25 g (1.00 mmol) of compound 4, 0.797 g (4.00 mmol) of compound 5 synthesized by the method described in Synthetic Communications, 1995, 25(19), 3045., 40 mL of chloroform, and 2.02 g (20.0 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 16 hours.

[0463] The reaction mixture was cooled, and water was added thereto, and the organic layer was washed with an aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure.

[0464] The obtained crude product was purified by a silica gel column to obtain 654 mg (0.405 mmol, yield 40.5%) of Compound 6 (Compound N-1) as a dark green solid.

[0465] The NMR spectrum of the obtained compound N-1 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.67 (d, J HH =15.6Hz, 2H), 7.36 (s, 2H), 7.03 (s, 2H), 6.86 (s, 2H), 6.61 (d, J HH =15.6Hz, 2H), 1.90 (br, 8H), 1.75 (s, 12H), 1.26 (br, 80H), 0.86 (t, 12H).

[0466] <Synthesis Example 3> (Synthesis of Compound 8) Compound 8 represented by the following formula was synthesized from compound 7 represented by the following formula.

[0467] [ka]

[0468] Into a 1 L four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 13.30 g (24.50 mmol) of compound 7 synthesized by the method described in paragraph

[0203] of JP 2014-31364 A and 490 mL of tetrahydrofuran were placed, and the flask was cooled to 0°C.

[0469] Next, 4.361 g (24.50 mmol) of N-bromosuccinimide was added to the four-neck flask, and the mixture was stirred at 0° C. for 4 hours.

[0470] The resulting solution was then warmed to room temperature and stirred at room temperature for an additional 3 hours to react, after which the reaction was stopped by adding a 3% aqueous solution of sodium sulfite.

[0471] The resulting reaction solution was extracted with hexane, and then washed with water and a saturated aqueous sodium chloride solution.

[0472] Next, the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0473] The resulting crude product was purified using a silica gel column to obtain 10.1 g (16.2 mmol, yield 66.3%) of Compound 8 as a pale yellow oil.

[0474] The NMR spectrum of the obtained compound 8 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.44 (d, J HH =5.6Hz, 1H), 7.07 (d, J HH =5.6Hz, 1H), 6.95 (s, 1H), 2.16 (m, 2H), 1.72 (m, 2H), 1.21 (br, 40H), 0.86 (t, 6H).

[0475] <Synthesis Example 4> (Synthesis of Compound 10) Compound 10 represented by the following formula was synthesized using Compound 8 represented by the following formula and Compound 9.

[0476] [ka]

[0477] Into a 300 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 5.23 g (6.65 mmol) of compound 9 synthesized by the method described in paragraphs

[0139] to

[0141] of WO 2011 / 052709, 9.51 g (15.3 mmol) of compound 8, and 120 mL of tetrahydronaphthalene were placed, and the flask was degassed by bubbling argon gas through it for 30 minutes.

[0478] Next, 0.304 g (0.333 mmol, 5 mol%) of Tris(dibenzylideneacetone)dipalladium(0), 0.405 g (1.33 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and 13 mL of tetrahydronaphthalene were placed in a four-neck flask and stirred for 5 minutes.

[0479] Next, 22 mL of 3.0 M aqueous potassium phosphate solution was further added to the four-neck flask, and the reaction solution was stirred while being heated in an oil bath set at 75° C. for 1 hour.

[0480] After cooling the reaction mixture, 100 mL of water and 100 mL of hexane were added, and the mixture was further washed three times with water and once with a saturated aqueous sodium chloride solution.

[0481] The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0482] The obtained crude product was purified using a silica gel column to obtain 9.83 g (6.09 mmol, yield 91.7%) of Compound 10 as a deep red oil.

[0483] The NMR spectrum of the obtained compound 10 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.46 (d, J HH =5.2Hz, 1H), 7.45 (d, J HH =5.2Hz, 1H), 7.07 (d, J HH =5.2Hz, 1H), 7.06 (d, J HH =5.2Hz, 1H), 7.02 (s, 1H), 6.98 (s, 1H), 6.86 (s, 1H), 6.84 (s, 1H), 2.19 (m, 4H), 1.91 (m, 4H), 1.73 (m, 4H), 1.18 (br, 120H), 0.86 (t, 18H).

[0484] <Synthesis Example 5> (Synthesis of Compound 11) Compound 11 represented by the following formula was synthesized from compound 10 represented by the following formula.

[0485] [ka]

[0486] In a 300 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 9.68 g (6.00 mmol) of compound 10 and 120 mL of chloroform were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve the compound.

[0487] Next, 5.38 g (42.0 mmol) of (Chloromethylene)dimethyliminium Chloride was placed in a four-neck flask, and the mixture was stirred while being heated in an oil bath set at 65° C. for a total of 20 hours.

[0488] After cooling the reaction mixture, 100 mL of water was added, and the mixture was washed twice with saturated aqueous sodium chloride solution.

[0489] The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0490] The resulting crude product was purified using a silica gel column to obtain 5.90 g (3.53 mmol, yield 58.9%) of Compound 11 as a purple oil.

[0491] The NMR spectrum of the obtained compound 11 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.91 (s, 2H), 8.08 (s, 1H), 8.07 (s, 1H), 7.06 (s, 1H), 7.02 (s, 1H), 6.93 (s, 1H), 6.91 (s, 1H), 2.22 (m, 4H), 1.92 (m, 4H), 1.75 (m, 4H), 1.21 (br, 120H), 0.85 (t, 18H).

[0492] Example 2 (Synthesis of Compound N-2) Compound 13 (Compound N-2) represented by the following formula was synthesized using Compound 11 and Compound 12 represented by the following formula.

[0493] [ka]

[0494] Into a 200 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 2.25 g (1.35 mmol) of compound 11, 0.888 g (3.38 mmol) of compound 12 synthesized by the method described in Adv. Mater. 2017, 29, 1703080., 68 mL of chloroform, and 1.07 g (13.5 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0495] The resulting solution was cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and then washed twice with water and once with saturated aqueous sodium chloride solution.

[0496] Next, the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0497] The obtained crude product was purified using a silica gel column to obtain 1.91 g (0.886 mmol, yield 65.6%) of Compound 13 (Compound N-2) as a dark blue-green solid.

[0498] The NMR spectrum of the obtained compound N-2 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.90 (s, 1H), 8.89 (s, 1H), 8.81 (s, 1H), 8.17 (s, 1H), 7.99 (s, 1H), 7.98 (s, 1H), 7.11 (s, 1H), 7.07 (s, 1H), 6.98 (s, 1H), 6.98 (s, 1H), 2.25 (m, 4H), 1.94 (m, 4H), 1.77 (m, 4H), 1.24 (br, 120H), 0.86 (m, 18H).

[0499] <Synthesis Example 6> (Synthesis of Compound 14) Compound 14 represented by the following formula was synthesized from compound 2 represented by the following formula.

[0500] [ka]

[0501] In a 200 mL four-neck flask, the inside atmosphere of which had been replaced with nitrogen gas, 8.2 g (13.4 mmol) of compound 2 and 67 mL of tetrahydrofuran were placed, and the flask was cooled to 0° C. in an ice bath.

[0502] Next, 6.7 mL of a tetrahydrofuran solution (2.0 M) of iPrMgCl was slowly added dropwise to the four-neck flask, and the mixture was stirred for 1 hour while being kept at 0°C.

[0503] Next, in a separate container, 8.2 g (13.4 mmol) of compound 2 diluted with 67 mL of tetrahydrofuran and a solution of 363.2 mg (0.67 mmol) of [1,3-Bis(diphenylphosphino)propane]nickel(II) Dichloride were slowly added dropwise to the resulting reaction solution at 0° C., and the reaction solution was then warmed to room temperature. After stirring at room temperature for 2 hours, the reaction was stopped with 0.5 M hydrochloric acid.

[0504] The resulting solution was extracted with chloroform, and then washed twice with water and once with a saturated aqueous sodium chloride solution.

[0505] The resulting organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0506] The obtained crude product was purified by a silica gel column to obtain 2.14 g (4.04 mmol, 15% yield) of Compound 14 as an orange solid.

[0507] The NMR spectrum of the obtained compound 14 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 6.98 (d, J HH = 5.6Hz, 2H), 6.69 (s, 2H), 6.67 (d, J HH = 5.6Hz, 2H), 1.88-1.84 (m, 8H), 1.30-1.19 (m, 80H), 0.87 (t, 12H).

[0508] <Synthesis Example 7> (Synthesis of Compound 15) Compound 15 represented by the following formula was synthesized from compound 14 represented by the following formula.

[0509] [ka]

[0510] In a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 2.0 g (1.89 mmol) of compound 14 and 19 mL of dichloromethane were placed and dissolved.

[0511] Next, 0.72 g (5.66 mmol) of (Chloromethylene)dimethyliminium Chloride was placed in a four-neck flask, and the mixture was stirred while being heated in an oil bath set at 40° C. for 3 hours.

[0512] After cooling the reaction mixture, 20 mL of water was added, and the mixture was washed twice with saturated aqueous sodium chloride solution.

[0513] The resulting solution was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0514] The resulting crude product was purified using a silica gel column to obtain 1.83 g (1.64 mmol, 87% yield) of Compound 15 as a purple solid.

[0515] The NMR spectrum of the obtained compound 15 was analyzed, and the results are as follows. [ 1 H NMR (THF-d)] δ 9.73 (s, 2H), 7.37 (s, 2H), 7.10 (s, 2H), 1.98-1.86 (m, 8H), 1.44-1.23 (m, 80H), 0.84 (t, 12H).

[0516] Example 3 (Synthesis of Compound N-3) Compound 16 (Compound N-3) represented by the following formula was synthesized using Compound 12 represented by the following formula and Compound 15.

[0517] [ka]

[0518] In a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 0.6 g (0.54 mmol) of compound 15, 0.35 g (1.34 mmol) of compound 12, 8 mL of chloroform, and 0.02 g (0.27 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0519] The resulting solution was then cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and washed twice with water and once with saturated aqueous sodium chloride.

[0520] The resulting organic layer was then dried over magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure.

[0521] The obtained crude product was purified using a silica gel column to obtain 0.69 g (0.47 mmol, 87% yield) of Compound 16 (Compound N-3) as a dark blue-green solid.

[0522] The NMR spectrum of the obtained compound N-3 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.74 (s, 4H), 7.91 (s, 2H), 7.39 (s, 2H), 6.92 (s, 2H) 1.99-1.88 (m, 8H), 1.43-1.23 (m, 80H), 0.85 (t, 12H).

[0523] Example 4 (Synthesis of Compound N-4) Compound 17 (Compound N-4) represented by the following formula was synthesized using Compound 5 represented by the following formula and Compound 15.

[0524] [ka]

[0525] In a 100 mL three-necked flask, the inside atmosphere of which had been replaced with nitrogen gas, 0.6 g (0.54 mmol) of compound 15, 0.43 g (2.15 mmol) of compound 5, 8 mL of chloroform, and 0.85 g (10.8 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 7 hours.

[0526] The resulting reaction solution was cooled, water was added, and the organic layer was washed with an aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution.

[0527] Next, the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0528] The obtained crude product was purified by a silica gel column to obtain 243 mg (0.18 mmol, 34% yield) of Compound 17 (Compound N-4) as a dark blue solid.

[0529] The NMR spectrum of the obtained compound N-4 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.63 (d, J HH = 16Hz, 2H), 7.03 (s, 2H), 6.83 (s, 2H), 6.63 (d, J HH = 16Hz, 2H), 1.95-1.85 (m, 8H), 1.75 (s, 12H), 1.40-1.23 (m, 80H), 0.86 (t, 12H).

[0530] <Synthesis Example 8> (Synthesis of Compound 19) Compound 19 represented by the following formula was synthesized from compound 18 represented by the following formula.

[0531] [ka]

[0532] Into a 100 mL three-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 2.85 g (5.36 mmol) of compound 18 synthesized by the method described in paragraph

[0271] of WO 2011 / 052709 and 27 mL of dehydrated tetrahydrofuran were added, and the resulting solution was cooled to −70° C., after which 3.3 mL of n-butyllithium solution (1.64 mol / L, hexane solution) was added and the mixture was stirred for 2 hours.

[0533] Next, while the reaction solution was kept at −70° C., 0.83 g (8.04 mmol) of trimethoxyborane was added, and the mixture was stirred for 2 hours.

[0534] Next, 10 wt% aqueous acetic acid (30 mL) was added to the resulting reaction solution, and the mixture was separated using ethyl acetate to extract the organic layer. Toluene (20 mL) and 1.29 g (10.72 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol were added to the resulting organic layer, and the mixture was dehydrated using a Dean-Stark tube for 30 minutes. The solvent was then removed using a rotary evaporator to obtain 3.53 g of crude compound 19 as a green oil.

[0535] <Synthesis Example 9> (Synthesis of Compound 21) Compound 21 represented by the following formula was synthesized using compound 19 represented by the following formula and compound 20.

[0536] [ka]

[0537] Into a 100 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 3.53 g (5.36 mmol) of Compound 19, which was the unpurified crude product obtained in Synthesis Example 8, 1.2 g (2.23 mmol) of Compound 20 purchased from Luminescence Technology Corp., and 22 mL of tetrahydrofuran were placed, and the flask was degassed by bubbling argon gas through it for 30 minutes.

[0538] To the resulting reaction solution, 0.164 g (0.179 mmol, 8 mol%) of Tris(dibenzylideneacetone)dipalladium(0) and 0.109 g (0.357 mmol, 16 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate were added, and the mixture was stirred for 5 minutes.

[0539] Next, 22 mL of a 3.0 M aqueous potassium phosphate solution was further added to the reaction solution, and the resulting reaction solution was stirred while being heated in an oil bath set at 75°C for 1 hour.

[0540] Next, after cooling the reaction mixture, 100 mL of water and 100 mL of hexane were added, and the mixture was washed three times with water and once with a saturated aqueous sodium chloride solution.

[0541] The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting crude product was purified using a silica gel column to give 2.11 g (1.49 mmol, 67% yield) of compound 21 as a dark red oil.

[0542] The NMR spectrum of the obtained compound 21 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.94 (s, 1H), 7.03 (dd, J HH = 9.2Hz, 5.2Hz, 2H), 6.85 (s, 1H), 6.81 (s, 1H), 6.68 (dd, J HH = 5.2Hz, 1.6Hz, 2H), 4.37 (t, J HH = 6.8Hz, 2H), 1.95-1.78 (m, 10H), 1.44-1.22 (m, 100H), 0.86 (t, 15H).

[0543] <Synthesis Example 10> (Synthesis of Compound 22) Compound 22 represented by the following formula was synthesized from compound 21 represented by the following formula.

[0544] [ka]

[0545] In a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 1.5 g (1.06 mmol) of compound 21 and 11 mL of dichloromethane were added and dissolved.

[0546] Next, 0.41 g (3.19 mmol) of (Chloromethylene)dimethyliminium Chloride was added to the resulting reaction solution, and the mixture was heated and stirred in an oil bath set at 40° C. for 3 hours.

[0547] Next, the resulting reaction solution was cooled, and then 20 mL of water was added, followed by separation and washing twice with saturated aqueous sodium chloride solution.

[0548] The resulting solution was dried over magnesium sulfate and filtered. The solvent was distilled off under reduced pressure to obtain a crude product, which was purified using a silica gel column to obtain 1.44 g (0.98 mmol, 92% yield) of compound 22 as a purple solid.

[0549] The NMR spectrum of the obtained compound 22 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.78 (s, 1H), 9.77 (s, 1H), 7.95 (s, 1H), 7.29 (s, 1H), 7.28 (s, 1H), 6.90 (s, 1H), 6.86 (s, 1H), 4.39 (t, J HH = 7.2Hz, 2H), 1.97-1.79 (m, 10H), 1.46-1.22 (m, 100H), 0.86 (t, 15H).

[0550] Example 5 (Synthesis of Compound N-5) Compound 23 (Compound N-5) represented by the following formula was synthesized using Compound 22 represented by the following formula and Compound 12.

[0551] [ka]

[0552] In a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 1.4 g (0.98 mmol) of compound 22, 0.78 g (2.95 mmol) of compound 12, 20 mL of chloroform, and 0.04 g (0.49 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0553] The resulting solution was then cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and washed twice with water and once with saturated aqueous sodium chloride.

[0554] The organic layer was then dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The crude product was purified using a silica gel column to give 1.5 g (0.77 mmol, 95% yield) of Compound 23 (Compound N-5) as a black solid.

[0555] The NMR spectrum of the obtained compound N-5 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.57-8.51 (m, 4H), 7.81 (s, 1H), 7.77 (s, 1H), 7.73 (s, 1H), 7.29 (br, 2H), 6.96 (s, 1H), 6.88 (s, 1H), 4.50 (t, J HH = 7.2Hz, 2H), 2.08-1.93 (m, 10H), 1.59-1.20 (m, 100H), 0.83 (t, 15H).

[0556] Example 6 (Synthesis of Compound N-6) Compound 24 (Compound N-6) represented by the following formula was synthesized using Compound 11 represented by the following formula and Compound 5.

[0557] [ka]

[0558] In a 200 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 1.67 g (1.00 mmol) of compound 11, 0.797 g (4.00 mmol) of compound 5, 50 mL of chloroform, and 2.02 g (20.0 mmol) of triethylamine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 8 hours.

[0559] The resulting solution was then cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and washed twice with water and once with saturated aqueous sodium chloride.

[0560] The organic layer was then dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The crude product was purified using a silica gel column to give 1.52 g (0.749 mmol, 74.0% yield) of Compound 24 (Compound N-6) as a dark blue-green solid.

[0561] The NMR spectrum of the obtained compound N-6 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.783 (s, 1H), 7.779 (s, 1H), 7.72 (d, J HH = 7.2Hz, 1H), 7.68 (d, J HH = 7.2Hz, 1H), 7.07 (s, 1H), 7.04 (s, 1H), 6.94 (d, J HH = 7.2Hz, 2H), 7.07 (s, 1H), 6.71 (s, 1H), 6.69 (s, 1H), 2.20 (m, 4H), 1.94 (m, 4H), 1.79 (s, 12H)1.75 (m, 4H), 1.24 (br, 120H), 0.86 (m, 18H).

[0562] Example 7 (Synthesis of Compound N-7) Compound 26 (Compound N-7) represented by the following formula was synthesized using Compound 11 represented by the following formula and Compound 25.

[0563] [ka]

[0564] Into a 100 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 1.00 g (0.600 mmol) of compound 11, 0.345 g (1.50 mmol) of compound 25 purchased from Angene International, 30 mL of chloroform, and 0.475 g (6.00 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0565] The resulting solution was then cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and washed twice with water and once with saturated aqueous sodium chloride.

[0566] The organic layer was then dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The crude product was purified using a silica gel column to give 0.866 g (0.414 mmol, 68.9% yield) of Compound 26 (Compound N-7) as a dark blue-green solid.

[0567] The NMR spectrum of the obtained compound N-7 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.865 (s, 1H), 8.863 (s, 1H), 8.57 (m, 2H), 8.16 (s, 2H), 7.72 (m, 2H), 7.10 (s, 1H), 7.07 (s, 1H), 6.971 (s, 1H), 6.967 (s, 1H), 2.25 (m, 4H), 1.96 (m, 4H), 1.77 (m, 4H), 1.24 (br, 120H), 0.86 (m, 18H).

[0568] Example 8 (Synthesis of Compound N-8) Compound 28 (Compound N-8) represented by the following formula was synthesized using Compound 11 represented by the following formula and Compound 27.

[0569] [ka]

[0570] Into a 100 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 0.951 g (0.570 mmol) of compound 11, 0.332 g (1.71 mmol) of compound 27 purchased from Tokyo Chemical Industry Co., Ltd., 30 mL of chloroform, and 0.676 g (8.55 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0571] The resulting solution was then cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and then washed twice with water and once with saturated aqueous sodium chloride. The resulting organic layer was dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure.

[0572] The resulting crude product was purified using a silica gel column to obtain 0.975 g (0.482 mmol, 84.6% yield) of Compound 28 (Compound N-8) as a dark blue-green solid.

[0573] The NMR spectrum of the obtained compound N-8 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.875 (s, 1H), 8.872 (s, 1H), 8.74 (s, 1H), 8.72 (s, 1H), 8.14 (s, 2H), 7.97 (m, 2H), 7.81 (m, 4H), 7.10 (s, 1H), 7.06 (s, 1H), 6.96 (s, 2H), 2.24 (m, 4H), 1.94 (m, 4H), 1.76 (m, 4H), 1.20 (br, 120H), 0.86 (m, 18H).

[0574] Example 9 (Synthesis of Compound N-9) Compound 29 (Compound N-9) represented by the following formula was synthesized using Compound 4 represented by the following formula and Compound 12.

[0575] [ka]

[0576] Into a 100 mL four-neck flask, the inside atmosphere of which had been replaced with nitrogen gas, 1.63 g (1.30 mmol) of compound 4, 0.855 g (3.25 mmol) of compound 12, 26 mL of chloroform, and 0.950 g (12.0 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0577] The resulting solution was then cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and washed twice with water and once with saturated aqueous sodium chloride.

[0578] The resulting organic layer was then dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0579] The obtained crude product was purified using a silica gel column to obtain 1.33 g (0.745 mmol, yield 58.7%) of Compound 29 (Compound N-9) as a dark blue-green solid.

[0580] The NMR spectrum of the obtained compound N-9 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.723 (s, 2H), 8.718 (s, 2H), 7.91 (s, 2H), 7.39 (s, 2H), 7.38 (s, 2H), 6.90 (s, 2H), 1.93 (m, 8H), 1.23 (br, 80H), 0.86 (t, 12H).

[0581] <Synthesis Example 11> (Synthesis of Compound 30) Compound 30 represented by the following formula was synthesized from compound 14 represented by the following formula.

[0582] [ka]

[0583] A 100 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, was charged with 2.0 g (1.88 mmol) of compound 14 and 19 mL of tetrahydrofuran, and the flask was cooled to 0° C. in an ice bath. 0.75 g (3.96 mmol) of N-bromosuccinimide purchased from Tokyo Chemical Industry Co., Ltd. was added, and the mixture was stirred at room temperature for 2 hours. The reaction was then quenched with a saturated aqueous solution of sodium thiosulfate.

[0584] The resulting solution was extracted with chloroform, washed twice with water, and once with a saturated aqueous solution of sodium chloride. The resulting organic layer was dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure.

[0585] The resulting crude product was then purified using a silica gel column to obtain 2.11 g (1.73 mmol, 92% yield) of Compound 30 as a red solid.

[0586] <Synthesis Example 12> (Synthesis of Compound 32) Compound 32 represented by the following formula was synthesized from compound 31 represented by the following formula.

[0587] [ka]

[0588] In a 200 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 4.5 g (39.4 mmol) of compound 31, 15.3 g (118.3 mmol) of 2-ethylhexanol purchased from Tokyo Chemical Industry Co., Ltd., 0.68 g (3.94 mmol) of paratoluenesulfonic acid, and 95 mL of toluene were placed and stirred while heating in an oil bath at 100° C. for 2 hours. The resulting solution was cooled to room temperature, and the reaction was quenched by adding water.

[0589] The resulting solution was extracted with chloroform, washed twice with water, and once with a saturated aqueous solution of sodium chloride. The resulting organic layer was dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure.

[0590] The resulting crude product was then purified using a silica gel column to obtain 7.8 g (36.7 mmol, 93% yield) of Compound 32 as a colorless oil.

[0591] <Synthesis Example 13> (Synthesis of Compound 34) Compound 34 represented by the following formula was synthesized using compound 32 represented by the following formula and compound 33.

[0592] [ka]

[0593] In a 100 mL three-necked flask, the inside atmosphere of which had been replaced with nitrogen gas, 1.52 g (7.16 mmol) of compound 32 and 30 mL of dehydrated tetrahydrofuran were added, and the solution was cooled to −70° C. After that, 3.3 mL of n-butyllithium solution (2.6 mol / L, hexane solution) was added and stirred for 2 hours.

[0594] Next, while the reaction solution was kept at −70° C., 2.0 g (10.74 mmol) of Compound 33 purchased from Tokyo Chemical Industry Co., Ltd. was added, and the mixture was stirred for 2 hours.

[0595] Next, the resulting reaction solution was warmed to room temperature, and then the reaction was stopped with a saturated aqueous ammonium chloride solution. The solution was separated using ethyl acetate, and the organic layer was extracted.

[0596] The resulting organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain 2.34 g of crude compound 34 as a colorless oil.

[0597] <Synthesis Example 14> (Synthesis of Compound 35) Compound 35 represented by the following formula was synthesized using compound 34 represented by the following formula and compound 30.

[0598] [ka]

[0599] Into a 100 mL four-neck flask, the inside atmosphere of which had been replaced with nitrogen gas, 1.27 g (2.63 mmol) of compound 34, 1.45 g (1.19 mmol) of compound 30, and 5 mL of tetrahydrofuran were placed, and the flask was degassed by bubbling argon gas through it for 30 minutes.

[0600] Next, 0.044 g (0.05 mmol, 8 mol%) of Tris(dibenzylideneacetone)dipalladium(0) and 0.058 g (0.19 mmol, 16 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate were added to the resulting reaction solution, and the mixture was stirred for 5 minutes.

[0601] Next, 5 mL of 3.0 M potassium phosphate aqueous solution was added to the reaction solution, and the reaction solution was stirred while heating for 1 hour in an oil bath set at 65°C. After cooling, 100 mL of water and 100 mL of hexane were added to the reaction solution, and the mixture was washed three times with water and once with saturated aqueous sodium chloride. The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0602] The resulting crude product was purified using a silica gel column to obtain 1.51 g (1.02 mmol, 86% yield) of Compound 35 as a deep red oil.

[0603] <Synthesis Example 15> (Synthesis of Compound 36) Compound 36 represented by the following formula was synthesized from compound 35 represented by the following formula.

[0604] [ka]

[0605] In a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 0.43 g (0.29 mmol) of compound 35 and 5 mL of dichloromethane were added and dissolved.

[0606] Next, 0.12 g (0.94 mmol) of (Chloromethylene)dimethyliminium Chloride was added to the resulting solution, and the mixture was stirred while being heated in an oil bath set at 40° C. for 3 hours.

[0607] The resulting solution was cooled, 5 mL of water was added, and the mixture was washed twice with saturated aqueous sodium chloride solution. The resulting solution was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0608] The resulting crude product was purified using a silica gel column to obtain 0.35 g (0.23 mmol, yield 78.6%) of Compound 36 as a purple solid.

[0609] Example 10 (Synthesis of Compound N-10) Compound 37 (Compound N-10) represented by the following formula was synthesized using Compound 36 represented by the following formula and Compound 12.

[0610] [ka]

[0611] Into a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 0.35 g (0.23 mmol) of compound 36, 0.32 g (1.23 mmol) of compound 12, 10 mL of chloroform, and 0.002 g (0.025 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0612] The resulting solution was then cooled to room temperature and water was added to quench the reaction. The resulting solution was extracted with chloroform and washed twice with water and once with saturated aqueous sodium chloride.

[0613] The resulting organic layer was then dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0614] The obtained crude product was purified by a silica gel column to obtain 0.4 g (0.197 mmol, yield 85.9%) of Compound 37 (Compound N-10) as a black solid.

[0615] The NMR spectrum of the obtained compound N-10 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.71 (s, 2H), 8.66 (s, 2H), 8.04 (s, 2H), 7.89 (s, 2H), 7.48 (br, 2H), 6.78 (s, 2H), 3.94 (d, 4H), 2.01-1.80 (m, 8H), 1.70-0.97 (m, 46H), 0.91-0.76 (m, 32H).

[0616] <Synthesis Example 16> (Synthesis of Compound 39) Compound 39 represented by the following formula was synthesized using compound 38 represented by the following formula and compound 19.

[0617] [ka]

[0618] Into a 200 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 1.08 g (2.00 mmol) of compound 38 synthesized by the method described in JP 2013-213180 A, 3.36 g (4.60 mmol) of compound 12, and 67 mL of tetrahydrofuran were placed, and the flask was degassed by bubbling nitrogen gas through it for 30 minutes.

[0619] Next, 0.0916 g (0.100 mmol, 5 mol%) of Tris(dibenzylideneacetone)dipalladium(0) and 0.116 g (0.400 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate were placed in a four-neck flask and stirred for 5 minutes.

[0620] Next, 6.7 mL of a 3.0 M aqueous potassium phosphate solution was added to the four-neck flask, and the reaction solution was stirred while being heated in an oil bath set at 76° C. for 1 hour.

[0621] After cooling the reaction mixture, 100 mL of water and 100 mL of heptane were added to a four-necked flask, and the organic layer was separated and washed three times with water and once with a saturated aqueous sodium chloride solution.

[0622] The resulting solution was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting crude product was purified using a silica gel column to give 2.55 g (1.77 mmol, 88.5% yield) of compound 39 as a deep red-purple oil.

[0623] The NMR spectrum of the obtained compound 39 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.13 (s, 2H), 7.51 (s, 2H), 7.11 (s, 1H), 7.09 (s, 1H), 6.70 (s, 1H), 6.69 (s, 1H), 2.76 (m, 4H), 1.95 (m, 8H), 1.69-1.62(m, 4H), 1.45-1.22 (br, 92H), 0.93-0.82 (m, 18H)

[0624] <Synthesis Example 17> (Synthesis of Compound 40) Compound 40 represented by the following formula was synthesized using compound 39 represented by the following formula.

[0625] [ka]

[0626] Into a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 2.52 g (1.75 mmol) of compound 39 and 88 mL of dichloromethane were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 39.

[0627] Next, 1.12 g (8.75 mmol) of (Chloromethylene)dimethyliminium Chloride was placed in a four-neck flask, and the mixture was stirred while being heated in an oil bath set at 49° C. for 7.5 hours.

[0628] The reaction mixture was cooled, and then 18 mL of water was added. The organic layer was washed twice with a saturated aqueous solution of sodium bicarbonate. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure.

[0629] The obtained crude product was purified using a silica gel column to obtain 2.54 g (1.70 mmol, yield 97.0%) of Compound 40 as a deep red-purple oil.

[0630] The NMR spectrum of the obtained compound 40 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.81 (s, 2H), 8.11 (s, 2H), 7.53 (s, 2H), 7.30 (s, 2H), 2.77(t, J HH =8.0Hz,4H), 1.99-1.94 (m, 8H), 1.72-1.62 (m, 4H), 1.45-1.21 (br, 92H), 0.91(t, J HH =7.0Hz,6H), 0.84(t, J HH =6.8Hz,12H).

[0631] Example 11 (Synthesis of Compound N-11) Compound 41 (N-11) represented by the following formula was synthesized using compound 40 represented by the following formula and compound 12.

[0632] [ka]

[0633] In a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 0.748 g (0.500 mmol) of compound 40, 0.395 g (1.50 mmol) of compound 12, 25 mL of chloroform, and 0.396 g (5.00 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 68°C for 1 hour.

[0634] The resulting solution was then cooled to room temperature and added to 150 mL of methanol, and the resulting solution was filtered to obtain a crude product as a precipitate.

[0635] The obtained crude product was purified by a silica gel column to obtain 0.882 g (0.444 mmol, yield 88.8%) of Compound 41 (Compound N-11) as a black solid.

[0636] The NMR spectrum of the obtained compound N-11 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.63 (s, 2H), 8.60 (s, 2H), 7.85 (s, 2H), 7.48 (s, 2H), 7.24 (s, 2H), 2.80(t, J HH =7.9Hz,4H), 1.98 (br, 8H), 1.79-1.69 (m, 4H), 1.56-1.21 (br, 92H), 0.97(t, J HH =6.9Hz,6H), 0.83(t, J HH =6.9Hz,12H).

[0637] <Synthesis Example 18> (Synthesis of Compound 43) Compound 43 represented by the following formula was synthesized using compound 19 represented by the following formula and compound 42.

[0638] [ka]

[0639] A 100 mL three-neck flask was charged with 1.00 g (2.36 mmol) of compound 42 (Tokyo Chemical Industry Co., Ltd.), 4.14 g (4.96 mmol) of compound 19, and 23.6 mL of THF, and the mixture was degassed by bubbling with argon gas for 30 minutes.

[0640] Next, 0.087 g (0.09 mmol, 4 mol%) of Tris(dibenzylideneacetone)dipalladium(0), 0.056 g (0.19 mmol, 8 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and 23.6 mL of 3.0 M aqueous potassium phosphate solution were added, and the temperature was raised to 40°C.

[0641] The resulting reaction solution was cooled, diluted with toluene, and the organic layer was washed twice with water.

[0642] The resulting solution was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by a silica gel column to obtain 1.87 g (yield 59.8%, 1.41 mmol) of Compound 43 as a black solid.

[0643] The NMR spectrum of the obtained compound 43 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.60 (s, 2H), 7.05 (d, J HH =5.6Hz, 2H), 6.66 (d, J HH=5.6Hz, 2H), 3.56 (t, 2H), 1.92-1.88 (m, 9H), 1.38-1.21 (m, 88H), 0.95-0.83 (m, 18H).

[0644] <Synthesis Example 19> (Synthesis of Compound 44) Compound 44 represented by the following formula was synthesized using compound 43 represented by the following formula.

[0645] [ka]

[0646] In a 100 mL three-neck flask whose internal atmosphere had been replaced with nitrogen gas, 1.49 g (1.13 mmol) of compound 43, 56.3 mL of dehydrated chloroform, and 0.552 g (4.32 mmol) of (Chloromethylene)dimethyliminium Chloride were placed, the internal temperature was raised to 61°C, and the mixture was stirred for 16 hours.

[0647] Next, the resulting reaction solution was cooled, and then water was added, and the organic layer was separated and washed twice with a saturated aqueous solution of sodium bicarbonate. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0648] The resulting crude product was purified using a silica gel column to obtain 1.31 g (yield 84.4%, 0.95 mmol) of Compound 44 as a black oil.

[0649] The NMR spectrum of the obtained compound 44 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.73 (s, 2H), 7.77 (s, 2H), 7.28 (s, 2H), 3.56 (t, 2H), 1.94-1.90 (m, 9H), 1.52-1.09 (m, 88H), 0.87-0.73 (m, 18H).

[0650] Example 12 (Synthesis of Compound N-12) Compound 45 (N-12) represented by the following formula was synthesized using compound 44 represented by the following formula and compound 12.

[0651] [ka]

[0652] In a 50 mL two-neck flask were placed 0.500 g (0.363 mmol) of compound 44, 18.0 g of dehydrated chloroform, 0.286 g (1.088 mmol) of compound 12, and 0.287 g (3.63 mmol) of pyridine, and the mixture was heated to 60°C in an oil bath.

[0653] After stirring for 3 hours, the mixture was allowed to cool to room temperature, and the reaction mixture was washed three times with 10 g of water. The organic layer was then dried over magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product.

[0654] The resulting crude product was purified by recycling preparative GPC to obtain 0.350 g (52% yield, 0.187 mmol) of compound 45 (N-12) as a black solid.

[0655] The NMR spectrum of the obtained compound N-12 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.71 (m, 4H), 7.91 (s, 2H), 7.71 (s, 2H), 7.31 (br, 2H), 3.60 (t, 2H), 2.11-1.77 (m, 9H), 1.50-1.06 (m, 88H), 0.98-0.82 (m, 18H).

[0656] <Synthesis Example 20> (Synthesis of Compound 47) Compound 47 represented by the following formula was synthesized using compound 19 represented by the following formula and compound 46.

[0657] [ka]

[0658] Into a 100 mL three-neck flask were placed 8.34 g (10.00 mmol) of compound 19, 1.71 g (4.17 mmol) of compound 46 (Tokyo Chemical Industry Co., Ltd.), and 41.7 mL of tetrahydrofuran, and the mixture was degassed by bubbling with argon gas for 30 minutes.

[0659] Next, 0.305 g (0.33 mmol, 4 mmol%) of Tris(dibenzylideneacetone)dipalladium(0), 0.203 g (0.67 mmol, 8 mmol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and 41.7 mL of 3.0 M potassium phosphate aqueous solution were added, and the temperature was then raised to 60°C.

[0660] The reaction mixture was then stirred for 2 hours and then cooled to room temperature. Next, the organic layer was extracted, diluted with hexane, washed twice with water, dried over magnesium sulfate, filtered, and then totally concentrated using a rotary evaporator.

[0661] Further purification using a silica gel column gave 5.56 g (yield) of Compound 47 as an orange oil.

[0662] The NMR spectrum of the obtained compound 47 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 6.98 (d, J HH =6.4Hz, 2H), 6.71 (s, 2H), 6.67 (d, J HH =6.4Hz, 2H), 2.68 (t, 4H), 1.86 (m, 8H), 1.57 (m, 4H), 1.22 (m, 92H), 0.88 (m, 18H).

[0663] <Synthesis Example 21> (Synthesis of Compound 48) Compound 48 represented by the following formula was synthesized using compound 47 represented by the following formula.

[0664] [ka]

[0665] In a 200 mL three-neck flask, the inside atmosphere of which had been replaced with nitrogen gas, 1.61 g (1.23 mmol) of compound 47, 61.4 mL of dehydrated chloroform, and 0.472 g (3.69 mmol) of (Chloromethylene)dimethyliminium Chloride were placed and stirred at an internal temperature of 60°C for 2 hours.

[0666] After cooling the reaction mixture, water was added, and the organic layer was separated and washed twice with saturated aqueous sodium hydrogen carbonate solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0667] The obtained crude product was purified by a silica gel column to obtain 1.22 g (yield 72.7%, 0.89 mmol) of Compound 48 as a reddish-black oil.

[0668] The NMR spectrum of the obtained compound 48 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.76 (s, 2H), 7.27 (s, 2H), 6.75 (s, 2H), 2.70 (t, 4H), 1.89 (m, 8H), 1.56 (m, 4H), 1.22 (m, 92H), 0.85 (m, 18H).

[0669] Example 13 (Synthesis of Compound N-13) Compound 49 (N-13) represented by the following formula was synthesized using compound 48 represented by the following formula and compound 12.

[0670] [ka]

[0671] A 50 mL two-necked flask was charged with 0.80 g (0.586 mmol) of compound 48, 29.0 g of dehydrated chloroform, 0.462 g (1.76 mmol) of compound 12, and 0.463 g (5.86 mmol) of pyridine, and the flask was placed in an oil bath heated to 60°C and stirred for 2 hours.

[0672] After cooling, the mixture was separated and washed with 87 g of water, and then the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0673] The obtained crude product was purified by a silica gel column to obtain 0.636 g (yield 58%, 0.342 mmol) of compound 49 (N-13) as a black solid.

[0674] The NMR spectrum of the obtained compound N-13 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.75 (s, 2H,), 8.73 (s, 2H), 7.89 (s, 2H), 7.39 (s, 2H), 6.86 (s, 2H), 2.77 (t, 4H), 1.92 (m, 8H), 1.60 (m, 4H), 1.21 (m, 92H), 0.93 (m, 6H), 0.85 (m, 12H).

[0675] <Synthesis Example 22> (Synthesis of Compound 51) Compound 51 represented by the following formula was synthesized using compound 19 represented by the following formula and compound 50.

[0676] [ka]

[0677] A 10 mL four-neck flask was charged with 1.2 g (4.05 mmol) of compound 50 (Tokyo Chemical Industry Co., Ltd.), 3.15 g (4.05 mmol) of compound 19, and 40.5 mL of tetrahydrofuran, and the contents were degassed by bubbling with nitrogen gas for 30 minutes.

[0678] Next, after cooling to 0°C in an ice bath, 0.111 g (0.12 mmol) of Tris(dibenzylideneacetone)dipalladium(0), 0.074 g (0.24 mmol) of Tri-tert-butylphosphonium Tetrafluoroborate, and 40.5 mL of 3.0 M aqueous potassium phosphate solution were added in this order.

[0679] After stirring for 4 hours, the temperature was raised to room temperature, and the reaction solution was diluted with water and chloroform and separated and washed to obtain an organic layer.

[0680] Next, the obtained organic layer was washed once each with water and saturated brine, dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure.

[0681] The obtained crude product was purified by a silica gel column to obtain 2.43 g (yield 80.5%) of Compound 51 as a black solid.

[0682] The NMR spectrum of the obtained compound 51 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.57 (s, 1H), 8.27 (s, 1H), 7.11 (d, J HH =5.6Hz, 1H), 6.69 (d, J HH =5.6Hz, 1H), 1.96 (m, 4H), 1.19-1.49 (m, 40H), 0.82-0.89 (m, 6H).

[0683] <Synthesis Example 23> (Synthesis of Compound 53) Compound 53 represented by the following formula was synthesized using compound 51 represented by the following formula and compound 52.

[0684] [ka]

[0685] A 100 mL four-neck flask was charged with 2.29 g (2.84 mmol) of 51, 1.12 g (1.42 mmol) of compound 52 synthesized by the method described in WO 2014 / 112656, and 14.2 mL of tetrahydrofuran, and the mixture was degassed by bubbling nitrogen gas through it for 30 minutes.

[0686] Next, 0.039 g (0.04 mmol) of Tris(dibenzylideneacetone)dipalladium(0), 0.026 g (0.09 mmol) of Tri-tert-butylphosphonium Tetrafluoroborate, and 14.2 mL of 3.0 M aqueous potassium phosphate solution were added in this order, and the mixture was placed in a 40°C oil bath to raise the temperature.

[0687] The resulting reaction mixture was stirred for 3 hours and then allowed to cool to room temperature. The resulting reaction mixture was diluted with water and chloroform, and the organic layer was separated and washed using a separatory funnel. The organic layer was washed once with aqueous acetic acid and once with saturated brine, dried over magnesium sulfate, and filtered. The solvent was then distilled off under reduced pressure.

[0688] The obtained crude product was dissolved in hexane, and then acetone was added thereto. The precipitated solid was filtered to obtain 2.14 g (yield 81%, 1.15 mmol) of Compound 53 as a blue-black solid.

[0689] The NMR spectrum of the obtained compound 53 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.71 (d, J HH =4.8Hz, 2H), 8.26 (d, J HH=4.8Hz, 2H), 7.81 (s, 1H),7.73 (s, 1H), 7.10 (m, 2H), 6.69 (d, 2H), 1.94-2.04 (m, 12H), 1.20-1.51 (m, 120H), 0.81-0.86 (m, 18H).

[0690] <Synthesis Example 24> (Synthesis of Compound 54) Compound 54 represented by the following formula was synthesized using compound 53 represented by the following formula.

[0691] [ka]

[0692] In a 50 mL two-neck flask, the inside atmosphere of which had been replaced with argon gas, 1.02 g (0.55 mmol) of compound 53, 27.5 mL of chloroform, and 0.211 g (1.65 mmol) of (Chloromethylene)dimethyliminium Chloride were placed, and the temperature was raised to 60°C.

[0693] After cooling, water was added to the reaction mixture, and the organic layer was separated and washed twice with a saturated aqueous solution of sodium bicarbonate. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0694] The obtained crude product was purified by a silica gel column to obtain 0.979 g (yield 92.9%, 0.191 mmol) of Compound 54 as a black solid.

[0695] The NMR spectrum of the obtained compound 54 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.7 (s, 1H), 9.75 (s, 1H), 8.66 (s, 2H), 8.25 (s, 1H), 8.23 ​​(s, 1H), 7.83 (s, 1H), 7.72 (s, 1H), 7.28 (s, 1H), 7.26 (s, 1H), 1.99-2.07 (m, 12H), 1.18-1.51 (m, 120H), 0.79-0.86 (m, 18H).

[0696] Example 14 (Synthesis of Compound N-14) Compound 55 (Compound N-14) represented by the following formula was synthesized using Compound 54 represented by the following formula and Compound 12.

[0697] [ka]

[0698] In a 50 mL two-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 0.622 g (0.322 mmol) of compound 54, 16 g of dehydrated chloroform, 0.257 g of compound 12, and 0.257 g of pyridine were placed, and the flask was placed in an oil bath heated to 60°C to raise the temperature.

[0699] After stirring for 4 hours, the mixture was cooled to room temperature, diluted with 70 g of chloroform, and purified with a silica gel column to obtain 0.675 g (yield 86.3%, 0.28 mmol) of compound 55 (compound N-14) as a black solid.

[0700] The NMR spectrum of the obtained compound N-14 was analyzed, and the results are as follows. [ 1 H NMR (O-DICHLOROBENZENE-D4)] δ 8.46-8.66 (m, 9H), 8.03 (s, 1H), 7.83(s, 1H), 7.68 (s, 2H), 7.42 (m, 2H), 2.14-2.23 (m, 12H), 1.29-1.66 (m, 120H), 0.77 (m, 18H).

[0701] <Synthesis Example 25> (Synthesis of Compound 56) Compound 56 represented by the following formula was synthesized using compound 55 represented by the following formula.

[0702] [ka]

[0703] In a 300 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 4.00 g (7.77 mmol) of compound 55, synthesized by the method described in the literature (Dyes and Pigments, 2015, 112, 145.), and 78 mL of tetrahydrofuran were placed and cooled to -30°C.

[0704] Next, 1.31 g (7.38 mmol) of N-bromosuccinimide was added to the four-neck flask, and the mixture was stirred at −30° C. for 6 hours.

[0705] The resulting solution was then warmed to room temperature and stirred at room temperature for an additional 3 hours to react, after which the reaction was stopped by adding a 3% aqueous solution of sodium sulfite.

[0706] The resulting reaction solution was extracted with hexane, and then washed with water and a saturated aqueous sodium chloride solution to obtain an organic layer.

[0707] Next, the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0708] The obtained crude product was purified using a silica gel column to obtain 4.16 g (7.01 mmol, yield 94.9%) of Compound 56 as a pale yellow oil.

[0709] The NMR spectrum of the obtained compound 56 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.16 (d, J HH=8.4Hz, 4H),7.10 (d, J HH =8.4Hz, 4H), 6.98 (d, J HH =4.8Hz, 1H), 6.75 (d, J HH =4.8Hz, 1H), 6.42 (s, 1H), 2.58 (t, 4H), 1.63−1.57(m, 4H), 1.36−1.27 (br, 12H), 0.87 (t, 6H).

[0710] <Synthesis Example 26> (Synthesis of Compound 57) Compound 57 represented by the following formula was synthesized using compound 56 represented by the following formula.

[0711] [ka]

[0712] Into a 100 mL three-necked flask, the inside atmosphere of which had been replaced with nitrogen gas, 4.13 g (6.96 mmol) of compound 56 and 70 mL of dehydrated tetrahydrofuran were added, and the resulting solution was cooled to −70° C. After that, 4.13 mL of n-butyllithium solution (1.64 mol / L, hexane solution) was added, and the mixture was stirred for 1 hour.

[0713] Next, while the reaction solution was kept at −70° C., 1.01 g (9.74 mmol) of trimethoxyborane was added, and the mixture was stirred for 2 hours.

[0714] Next, 10% by weight aqueous acetic acid (30 mL) was added to the resulting reaction solution, and the mixture was separated using ethyl acetate to extract the organic layer. Toluene (20 mL) and 1.25 g (10.4 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol were added to the resulting organic layer, and the mixture was dehydrated using a Dean-Stark tube for 30 minutes. The solvent was then removed using a rotary evaporator to obtain 4.47 g of crude compound 57 as a green oil.

[0715] <Synthesis Example 27> (Synthesis of Compound 59) Compound 59 represented by the following formula was synthesized using compound 57 and compound 58 represented by the following formula.

[0716] [ka]

[0717] Into a 300 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 1.00 g (1.43 mmol) of compound 58 synthesized by the method described in JP 2013-43818 A, 2.20 g (3.43 mmol) of compound 57, and 14 mL of tetrahydrofuran were placed, and the flask was degassed by bubbling argon gas through it for 30 minutes.

[0718] Next, 0.105 g (0.11 mmol, 8 mol%) of Tris(dibenzylideneacetone)dipalladium(0), 0.070 g (0.23 mmol, 16 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and 5 mL of tetrahydrofuran were placed in a four-neck flask and stirred for 5 minutes.

[0719] Next, 14 mL of a 3.0 M aqueous potassium phosphate solution was added to the four-neck flask, and the reaction solution was stirred while being heated in an oil bath set at 50° C. for 3 hours.

[0720] After cooling the reaction mixture, 100 mL of water and 100 mL of hexane were added to a four-necked flask, and the organic layer was separated and washed three times with water and once with a saturated aqueous sodium chloride solution.

[0721] The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by a silica gel column to obtain 1.74 g (1.11 mmol, 78% yield) of Compound 59 as a red oil.

[0722] The NMR spectrum of the obtained compound 59 was analyzed, and the results are as follows. [1 H NMR (CDCl)] δ 7.38 (s, 1H), 7.23−7.18 (m, 8H),7.14−7.10 (m, 8H),7.03−7.00 (m, 2H),6.92 (s, 1H),6.79−6.77 (m, 2H), 6.58 (s, 1H), 6.53 (s, 1H), 2.62-2.57 (m, 8H), 2.19-2.11 (m, 2H), 1.71-1.56 (m, 10H), 1.37-1.25 (m, 28H), 1.25-1.08 (br, 36H), 0.89-0.83 (m, 18H).

[0723] <Synthesis Example 28> (Synthesis of Compound 60) Compound 60 represented by the following formula was synthesized using compound 59 represented by the following formula.

[0724] [ka]

[0725] In a 100 mL three-necked flask whose internal atmosphere had been replaced with nitrogen gas, 1.74 g (1.11 mmol) of compound 59 and 12 mL of chloroform were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 59.

[0726] Next, 0.43 g (3.33 mmol) of (Chloromethylene)dimethyliminium Chloride was placed in a three-necked flask, and the mixture was stirred while being heated in an oil bath set at 65° C. for 2 hours.

[0727] The reaction mixture was cooled, and then 20 mL of water was added, and the organic layer was washed twice with a saturated aqueous solution of sodium chloride. The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0728] The resulting crude product was purified using a silica gel column to obtain 1.63 g (1.01 mmol, yield 90.6%) of Compound 60 as a deep red oil.

[0729] The NMR spectrum of the obtained compound 60 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.76 (s, 1H), 9.75 (s, 1H), 7.46 (s, 1H), 7.37 (s, 1H), 7.36 (s, 1H), 7.21−7.12 (m, 16H), 7.00 (s, 1H), 6.61 (s, 1H), 6.58 (s, 1H), 2.63−2.58 (m, 8H), 2.21−2.13(m, 2H), 1.73−1.57 (m, 10H), 1.37−1.26 (m, 28H), 1.24−1.09 (br, 36H), 0.89−0.83 (m, 18H).

[0730] Example 15 (Synthesis of Compound N-15) Compound 61 (Compound N-15) represented by the following formula was synthesized using Compound 12 represented by the following formula and Compound 60.

[0731] [ka]

[0732] In a 100 mL four-neck flask whose internal atmosphere had been replaced with nitrogen gas, 0.57 g (0.35 mmol) of compound 60, 0.28 g (1.05 mmol) of compound 12, 10 mL of chloroform, and 0.003 g (0.04 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0733] The resulting solution was cooled to room temperature, and the reaction was stopped by adding water. The resulting solution was extracted with chloroform, and then washed twice with water and once with saturated aqueous sodium chloride to obtain an organic layer.

[0734] Next, the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0735] The obtained crude product was purified by a silica gel column to obtain 0.64 g (0.30 mmol, yield 86.3%) of Compound 61 (Compound N-15) as a dark blue-green solid.

[0736] The NMR spectrum of the obtained compound N-15 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.74 (s, 1H), 8.73 (s, 1H), 8.69 (s, 1H), 8.68 (s, 1H), 7.91 (s, 1H), 7.90 (s, 1H), 7.49 (s, 2H), 7.46 (s, 1H), 7.21-7.14 (m, 16H), 7.03 (s, 1H), 6.67 (s, 1H), 6.64 (s, 1H), 2.64−2.59 (m, 8H), 2.24−2.17(m, 2H), 1.99−1.86 (m, 8H), 1.76−1.59 (m, 10H), 1.38―1.26 (m, 28H), 1.24―1.12 (br, 36H), 0.89―0.83 (m, 18H).

[0737] <Synthesis Example 29> (Synthesis of Compound 63) Compound 63 represented by the following formula was synthesized using compound 62 represented by the following formula.

[0738] [ka]

[0739] Into a 300 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 5.02 g (12.0 mmol) of compound 62 synthesized by the method described in paragraphs

[0261] to

[0271] of WO 2011 / 052709 and 100 mL of tetrahydrofuran were placed, and the flask was cooled to -30°C.

[0740] Next, 2.11 g (11.9 mmol) of N-bromosuccinimide was added to the four-neck flask, and the mixture was stirred at −30° C. for 6 hours.

[0741] The resulting solution was then warmed to room temperature and stirred at room temperature for an additional 3 hours to react, after which the reaction was stopped by adding a 3% aqueous solution of sodium sulfite.

[0742] The resulting reaction solution was extracted with hexane, and then washed with water and a saturated aqueous sodium chloride solution to obtain an organic layer.

[0743] Next, the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0744] The obtained crude product was purified using a silica gel column to obtain 4.66 g (9.36 mmol, yield 78.0%) of Compound 63 as a pale yellow oil.

[0745] The NMR spectrum of the obtained compound 63 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 6.98 (d, J HH =4.8Hz, 1H), 6.66 (s, 1H),6.65 (d, J HH =4.8Hz, 1H), 1.87-1.74(m, 4H), 1.41-1.23 (br, 24H), 0.86 (t, 6H).

[0746] <Synthesis Example 30> (Synthesis of Compound 64) Compound 64 represented by the following formula was synthesized using compound 63 represented by the following formula.

[0747] [ka]

[0748] Into a 100 mL three-necked flask, the inside atmosphere of which had been replaced with nitrogen gas, 4.59 g (9.23 mmol) of compound 63 and 90 mL of dehydrated tetrahydrofuran were added, and the resulting solution was cooled to −70° C. After that, 5.8 mL of n-butyllithium solution (1.64 mol / L, hexane solution) was added and stirred for 1 hour.

[0749] Next, while the reaction solution was kept at −70° C., 2.43 g (12.9 mmol) of trimethoxyborane was added, and the mixture was stirred for 2 hours.

[0750] Next, 10% by weight aqueous acetic acid (30 mL) was added to the resulting reaction solution, and the mixture was separated using ethyl acetate to extract the organic layer. Toluene (20 mL) and 1.66 g (13.82 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol were added to the resulting organic layer, and the mixture was dehydrated using a Dean-Stark tube for 30 minutes. The solvent was then removed using a rotary evaporator to obtain 5.00 g of crude compound 64 as a green oil.

[0751] <Synthesis Example 31> (Synthesis of Compound 66) Compound 66 represented by the following formula was synthesized using compound 64 represented by the following formula and compound 65.

[0752] [ka]

[0753] In a 200 mL four-neck flask, the internal atmosphere of which had been replaced with nitrogen gas, 1.65 g (2.80 mmol) of compound 65, which had been synthesized by the method described in the literature (ACS Omega 2017, 2, 4347.), 3.83 g (7.00 mmol) of compound 64, and 93 mL of tetrahydrofuran were placed, and the flask was degassed by bubbling argon gas through it for 30 minutes.

[0754] Next, 0.128 g (0.140 mmol, 5 mol%) of Tris(dibenzylideneacetone)dipalladium(0), 0.170 g (0.560 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and 5 mL of tetrahydrofuran were placed in a four-neck flask and stirred for 5 minutes.

[0755] Next, 9.3 mL of a 3.0 M aqueous potassium phosphate solution was added to the four-neck flask, and the reaction solution was stirred while being heated in an oil bath set at 50° C. for 3 hours.

[0756] After cooling the reaction mixture, 100 mL of water and 100 mL of hexane were added to a four-necked flask, and the organic layer was separated and washed three times with water and once with a saturated aqueous sodium chloride solution.

[0757] The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting crude product was purified using a silica gel column to give 3.21 g (2.54 mmol, 90.6% yield) of compound 66 as a red oil.

[0758] The NMR spectrum of the obtained compound 66 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 7.44 (s, 1H), 7.03 (d, J HH =4.0Hz, 1H), 7.02 (d, J HH =4.0Hz, 1H), 6.97 (s, 1H), 6.83 (s, 1H), 6.80 (s, 1H), 6.89 (d, J HH =4.8Hz, 1H), 6.68 (d, J HH =4.8Hz, 1H), 2.23-2.16(m, 2H), 1.94-1.81 (m, 8H), 1.77-1.69 (m, 2H), 1.44-1.11 (br, 72H), 0.86-0.80 (m, 18H).

[0759] <Synthesis Example 32> (Synthesis of Compound 67) Compound 67 represented by the following formula was synthesized using compound 66 represented by the following formula.

[0760] [ka]

[0761] In a 100 mL three-necked flask whose internal atmosphere had been replaced with nitrogen gas, 3.41 g (2.70 mmol) of compound 66 and 80 mL of chloroform were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 66.

[0762] Next, 1.04 g (8.10 mmol) of (Chloromethylene)dimethyliminium Chloride was placed in a three-necked flask, and the mixture was stirred while being heated in an oil bath set at 65° C. for 2 hours.

[0763] The reaction mixture was cooled, and then 20 mL of water was added, and the organic layer was washed twice with a saturated aqueous solution of sodium chloride. The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0764] The resulting crude product was purified using a silica gel column to obtain 2.97 g (2.25 mmol, yield 83.3%) of Compound 67 as a deep red solid.

[0765] The NMR spectrum of the obtained compound 67 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 9.79 (s, 1H), 9.78 (s, 1H), 7.53 (s, 1H), 7.29 (s, 1H), 7.28 (s, 1H), 7.06 (s, 1H), 6.87 (s, 1H), 2.25−2.17(m, 2H), 1.96-1.84 (m, 8H), 1.78-1.71 (m, 2H), 1.44-1.12 (br, 72H), 0.87-0.79 (m, 18H).

[0766] Example 16 (Synthesis of Compound N-16) Compound 68 (Compound N-16) represented by the following formula was synthesized using Compound 12 represented by the following formula and Compound 67.

[0767] [ka]

[0768] In a 100 mL four-neck flask, the inside atmosphere of which had been replaced with nitrogen gas, 0.858 g (0.650 mmol) of compound 67, 0.513 g (1.95 mmol) of compound 12, 30 mL of chloroform, and 0.514 g (6.50 mmol) of pyridine were placed, and the mixture was stirred while being heated in an oil bath at 65°C for 2 hours.

[0769] The resulting solution was cooled to room temperature, and the reaction was stopped by adding water. The resulting solution was extracted with chloroform, and then washed twice with water and once with saturated aqueous sodium chloride to obtain an organic layer.

[0770] Next, the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

[0771] The obtained crude product was purified by a silica gel column to obtain 0.967 g (0.534 mmol, yield 82.2%) of Compound 68 (Compound N-16) as a dark blue-green solid.

[0772] The NMR spectrum of the obtained compound N-16 was analyzed, and the results are as follows. [ 1 H NMR (CDCl)] δ 8.74 (s, 4H), 7.92 (s, 1H), 7.91 (s, 1H), 7.63 (s, 1H), 7.40 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 6.94 (s, 1H), 6.91 (s, 1H), 2.29-2.22(m, 2H), 1.99-1.86 (m, 8H), 1.82-1.75 (m, 2H), 1.44-1.14 (br, 72H), 0.92-0.80 (m, 18H).

[0773] <Preparation Example 1> (Preparation of Ink I-1) Polymer compound P-1, a p-type semiconductor material, was mixed with o-dichlorobenzene (ODCB) as a solvent to give a concentration of 0.8 wt % relative to the total weight of the ink, and compound N-1, an n-type semiconductor material, was mixed with the solvent to give a concentration of 0.8 wt % relative to the total weight of the ink (p-type semiconductor material / n-type semiconductor material = 1 / 1), and the resulting mixture was stirred at 60°C for 8 hours.The resulting mixture was then filtered using a filter to obtain ink (I-1).

[0774] <Preparation Example 2> (Preparation of Ink I-2) Polymer compound P-1, a p-type semiconductor material, was mixed with ODCB as a solvent to give a concentration of 1.2 wt % relative to the total weight of the ink, and compound N-2, an n-type semiconductor material, to give a concentration of 1.2 wt % relative to the total weight of the ink (p-type semiconductor material / n-type semiconductor material = 1 / 1). The mixture was stirred at 60°C for 8 hours, and the resulting mixture was filtered to give ink (I-2).

[0775] <Preparation Examples 3 to 17> (Preparation of Inks (I-3) to (I-17)) Inks (I-3) to (I-17) were prepared in the same manner as in Preparation Example 2, except that the p-type semiconductor material and n-type semiconductor material were used in the combinations shown in Table 5 below.

[0776] <Preparation Example 18> (Preparation of Ink I-18) Polymer compound P-1, a p-type semiconductor material, was mixed with o-xylene (oXY) to a concentration of 1.2 wt % relative to the total weight of the ink, and compound N-2, an n-type semiconductor material, was mixed to a concentration of 1.2 wt % relative to the total weight of the ink (p-type semiconductor material / n-type semiconductor material = 1 / 1). The mixture was stirred at 60°C for 8 hours, and the resulting mixture was filtered to obtain ink (I-18).

[0777] <Preparation Example 19> (Preparation of Ink I-19) A mixed solvent was prepared using o-xylene as the first solvent and acetophenone (AP) as the second solvent, with the volume ratio of the first solvent to the second solvent being 97:3. Polymer compound P-1, a p-type semiconductor material, was mixed with the mixed solvent to a concentration of 1.2 wt% relative to the total weight of the ink, and compound N-2, an n-type semiconductor material, was mixed with the mixed solvent to a concentration of 1.2 wt% relative to the total weight of the ink (p-type semiconductor material / n-type semiconductor material = 1 / 1). The mixture was stirred at 60°C for 8 hours, and the resulting mixture was filtered to obtain ink (I-19).

[0778] <Preparation Example 20> (Preparation of Ink I-20) A mixed solvent was prepared using o-xylene as the first solvent and methyl benzoate (MBZ) as the second solvent, with the volume ratio of the first solvent to the second solvent being 97:3. Polymer compound P-1, a p-type semiconductor material, was mixed with the mixed solvent to a concentration of 1.2 wt% relative to the total weight of the ink, and compound N-12, an n-type semiconductor material, was mixed with the mixed solvent to a concentration of 1.2 wt% relative to the total weight of the ink (p-type semiconductor material / n-type semiconductor material = 1 / 1). The mixture was stirred at 60°C for 8 hours, and the resulting mixture was filtered to obtain ink (I-20).

[0779] <Preparation Examples 21 to 24> (Preparation of Inks (I-21) to (I-24)) Inks (I-21) to (I-24) were prepared in the same manner as in Preparation Example 20, except that the p-type semiconductor material and n-type semiconductor material were used in the combinations shown in Table 5 below.

[0780] [Table 5]

[0781] Example 17 (Production and evaluation of photoelectric conversion element) (1) Manufacturing of photoelectric conversion elements and their encapsulated bodies A glass substrate on which a thin film (anode) of ITO was formed to a thickness of 50 nm by sputtering was prepared, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

[0782] Next, ink (I-1) was applied to the thin ITO film by spin coating to form a coating, which was then dried by heating for 10 minutes on a hot plate heated to 100°C under a nitrogen gas atmosphere to form an active layer (pre-baking step). The thickness of the formed active layer was approximately 150 nm.

[0783] Next, in a resistance heating deposition apparatus, a calcium (Ca) layer was formed on the formed active layer to a thickness of about 5 nm, to serve as an electron transport layer.

[0784] Next, a silver (Ag) layer was formed on the formed electron 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.

[0785] Next, a UV-curable sealant was applied to the glass substrate serving as the support substrate so as to surround the periphery of the manufactured photoelectric conversion element. After laminating the glass substrate serving as the sealing substrate, UV light was irradiated to seal the photodetector in the gap between the support substrate and the sealing substrate, thereby obtaining a sealed photoelectric conversion element. When viewed from the thickness direction, 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. The resulting sealed element was designated Sample 1.

[0786] (2) Evaluation of photoelectric conversion elements (external quantum efficiency) A reverse bias voltage of −5 V was applied to the manufactured Sample 1, and the external quantum efficiency (EQE) at this applied voltage was measured and evaluated using a solar simulator (CEP-2000, manufactured by Bunkoukeiki Co., Ltd.). The results are shown in Table 6 below.

[0787] Regarding EQE, first, a reverse bias voltage of -5 V was applied to the sealed body of the photoelectric conversion element, and a constant number of photons (1.0 × 10 16 The current value generated when the sample was irradiated with light from 1000 nm to 1200 nm was measured, and the EQE spectrum was determined in the wavelength range of 300 nm to 1200 nm by a known method.

[0788] Next, among the multiple measurement values ​​obtained every 20 nm, the measurement value at the wavelength (λmax) closest to the absorption peak wavelength was taken as the EQE value (%).

[0789] Example 18 (Production and evaluation of photoelectric conversion element) A sealed photoelectric conversion element was produced and evaluated in the same manner as in Example 17, except that ink (I-2) was used instead of ink (I-1) and the thickness of the formed active layer was approximately 300 nm. The results are shown in Table 6 below.

[0790] <Examples 19 to 40> (Production and evaluation of photoelectric conversion element) Except for using inks (I-3) to (I-24) instead of ink (I-2), sealed photoelectric conversion elements were produced and evaluated in the same manner as in Example 18. The results are shown in Table 6 below.

[0791] [Table 6]

[0792] <Examples 41 to 48> Evaluation of photoelectric conversion element (heat resistance) The photoelectric conversion elements according to Examples 17 to 21, 24 to 25, and 33 produced as described above were each evaluated for heat resistance using EQE as an index.

[0793] Specifically, the EQE value of a photoelectric conversion element (sample 1) that had undergone only the pre-baking step, with the heating temperature in the pre-baking step already described set to 100° C., was used as a standard, and the EQE value was divided by the EQE value of a photoelectric conversion element (sample 2) that had also undergone a post-baking step with the heating temperature set to 220° C. to obtain a standardized value (EQE220° C. / EQE100° C.). The results are shown in Table 7 below.

[0794] Specifically, the post-baking step was carried out by heating Sample 1, which has already been described, for 50 minutes on a hot plate heated to 220° C. in a nitrogen gas atmosphere.

[0795] [Table 7]

[0796] As is clear from Table 7, for "Sample 2" according to Examples 41 to 48, all of the EQE 220℃ / EQE 100℃ However, the EQE was 0.85 or higher and reached 1.06 to 4.50, which indicates that the EQE value does not decrease when the heating temperature in the post-bake process is 220°C, and that the EQE tends to improve. Therefore, the heat resistance can be evaluated as "good (○)" in the range of 100°C to 220°C.

[0797] <Examples 49 to 53> Evaluation of photoelectric conversion element (heat resistance) The heat resistance of each of the photoelectric conversion elements according to Examples 36 to 40 produced as described above was evaluated using EQE as an index.

[0798] Specifically, the EQE value of a photoelectric conversion element (sample 1) that had undergone only the pre-baking step, with the heating temperature in the pre-baking step already described set to 100° C., was used as a standard, and the EQE value was divided by the EQE value of a photoelectric conversion element (sample 3) that had also undergone a post-baking step with the heating temperature set to 200° C. to obtain a standardized value (EQE200° C. / EQE100° C.). The results are shown in Table 8 below.

[0799] Specifically, the post-baking step was carried out by heat-treating Sample 1, which has already been described, for 50 minutes on a hot plate heated to 200° C. in a nitrogen gas atmosphere.

[0800] [Table 8]

[0801] As is clear from Table 8, for "Sample 3" according to Examples 49 to 53, all of the EQE 200℃ / EQE 100℃ However, the EQE was 0.85 or higher, reaching 0.85 to 1.54, which indicates that the EQE value hardly decreases and may even improve when the heating temperature in the post-bake process is 200°C. Therefore, the heat resistance can be evaluated as "good (○)" in the range of 100°C to 200°C.

[0802] <Example of comparative adjustment> Inks (C-1) and (C-2) were prepared in the same manner as in Preparation Example 1, except that the n-type semiconductor material and p-type semiconductor material were used in the combinations shown in Table 9 below.

[0803] [Table 9]

[0804] <Comparative Examples 1 and 2> Evaluation of photoelectric conversion element (heat resistance) Sealed photoelectric conversion elements were produced in the same manner as in Example 18, except that inks (C-1) and (C-2) were used instead of ink (I-2), and the heat resistance of each photoelectric conversion element was evaluated using EQE as an index in the same manner as in Examples 27 to 31. The results are shown in Table 10 below.

[0805] [Table 10]

[0806] As is clear from Table 10, the heat resistance of "Sample 2" according to Comparative Examples 1 and 2 was evaluated as "EQE" at least when heated to 220°C. 220℃ / EQE 100℃ Since the EQE value was less than 0.8, it was found that the EQE value was reduced by the heat treatment in the post-bake step at a heating temperature of 220°C. Therefore, the heat resistance of Comparative Examples 1 and 2, using EQE as an index, was evaluated as "poor (×)".

[0807] <Comparative Preparation Examples 3 and 4> Inks (C-3) and (C-4) were prepared in the same manner as in Preparation Example 20, except that the n-type semiconductor material and p-type semiconductor material were used in the combinations shown in Table 11 below.

[0808] [Table 11]

[0809] <Comparative Examples 3 and 4> Evaluation of photoelectric conversion element (heat resistance) Sealed photoelectric conversion elements were produced in the same manner as in Example 18, except that inks (C-3) and (C-4) were used instead of ink (I-2), and the heat resistance of each photoelectric conversion element was evaluated using EQE as an index in the same manner as in Examples 49 to 53. The results are shown in Table 12 below.

[0810] [Table 12]

[0811] As is clear from Table 12, the heat resistance of "Sample 4" according to Comparative Examples 3 and 4 was evaluated as "EQE" at least when heated to 200°C. 200℃ / EQE 100℃ Since the EQE value was less than 0.5, it was found that the EQE value was reduced by the heat treatment in the post-bake step at a heating temperature of 200°C. Therefore, the heat resistance of Comparative Examples 3 and 4, using EQE as an index, was evaluated as "poor (×)". [Explanation of symbols]

[0812] 1 Image detection unit 2 Display device 10 Photoelectric conversion element 11, 210 Support substrate 12 Anode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Cathode 17 Sealing member 20 CMOS transistor substrate 30 Interlayer insulating film 32 Interlayer wiring section 40 Sealing layer 42 Scintillator 44 Reflective layer 46 Protective layer 50 color filters 100 Fingerprint detection unit 200 Display panel 200a display area 220 Organic EL element 230 Touch Sensor Panel 240 Sealing substrate 300 Vein detection unit 302 Glass substrate 304 Light source section 306 Cover part 310 Insertion section 400 Image detector for TOF distance measuring device 402 Floating Diffusion Layer 404 Photogate 406 Light blocking part

Claims

1. A composition comprising a p-type semiconductor material and an n-type semiconductor material, and comprising a compound represented by the following formula (I) as the n-type semiconductor material: A １ -B １ -A １ (I) (In formula (I), A １ represents an electron-withdrawing group selected from the group consisting of groups represented by the following formula (a-1) and formula (a-5): 【Chemistry 1】 (In formulas (a-1) and (a-5), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and heterocyclic ring may be a single ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different. X 4 and X 5 each independently represent an oxygen atom, a sulfur atom, an alkylidene group, or a group represented by ═C(—CN) 2 . X 7 represents a hydrogen atom or a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group or a monovalent heterocyclic group. R a1 and R a2 each independently represent a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, an alkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group. B １ represents a divalent group containing two or more structural units that are linked by a single bond to form a π-conjugated system, and contains two or more first structural units represented by the following formula (III): 【Chemistry 2】 (In formula (III), X 1 and X 2 represent a sulfur atom. Z 1 and Z 2 each represent a group represented by ═CH—. Y represents a group represented by —C(═O)— or an oxygen atom. Each R is independently an alkyl group having 1 to 50 carbon atoms which may have a substituent, or represents an optionally substituted phenyl group. Multiple R's may be the same or different. The remaining second structural units other than the first structural units are a divalent group containing an unsaturated bond, an arylene group, or a heteroarylene group. Two A's １ may be different from each other. Two or more first constitutional units may be the same as or different from each other. When there are two or more second constitutional units, the two or more second constitutional units may be the same as or different from each other.

2. B １ The composition according to claim 1 , wherein the first constitutional unit is three or more.

3. The composition of claim 1 or 2, wherein the second constitutional unit is selected from the group consisting of a divalent group containing an unsaturated bond and a group represented by the following formula (IV-1) to formula (IV-9): 【Transformation 3】 (Formula (IV-1) to formula (IV-9), X １ and X ２ each independently represents a sulfur atom or an oxygen atom, Z １ and Z ２ each independently represents a group represented by ═C(R)— or a nitrogen atom, and Each R is independently hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, an optionally substituted cycloalkyl group, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an alkylthio group which may have a substituent; an optionally substituted cycloalkylthio group, an optionally substituted arylthio group; an optionally substituted monovalent heterocyclic group, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; an alkenyl group which may have a substituent; an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group; an optionally substituted cycloalkynyl group, cyano group, nitro group, a group represented by —C(═O)—R a , or represents a group represented by —SO 2 —R b , R a and R b are each independently hydrogen atoms, an alkyl group which may have a substituent, an optionally substituted aryl group; an alkyloxy group which may have a substituent; an optionally substituted aryloxy group, or represents a monovalent heterocyclic group which may have a substituent; When there are two R's, the two R's may be the same or different.

4. B １ The composition according to claim 1 , wherein is a divalent group in which 2 to 4 of the first structural units are linked together.

5. B １ is a divalent group having any one structure selected from the group consisting of structures represented by the following formulas (V-1) to (V-9): -CU1-CU2-CU1- (V-1) -CU1-CU2-CU1-CU2-CU1- (V-2) -CU2-CU1-CU2-CU1-CU2- (V-3) -CU1-CU2-CU1-CU2-CU1-CU2-CU1- (V-4) -CU1-CU1- (V-5) -CU2-CU1-CU2- (V-6) -CU1-CU1-CU1- (V-7) -CU2-CU1-CU1-CU2- (V-8) -CU2-CU1-CU1-CU1-CU2- (V-9) (In formulas (V-1) to (V-9), CU1 represents the first constitutional unit; CU2 represents the second constitutional unit. When there are two or more CU1s, the two or more CU1s may be the same as or different from each other, and when there are two or more CU2s, the two or more CU2s may be the same as or different from each other.

6. An ink comprising the composition according to any one of claims 1 to 5 and a solvent.

7. 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, wherein the active layer comprises the composition according to any one of claims 1 to 5.

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

9. An image sensor comprising the photoelectric conversion element according to claim 7 .

10. A fingerprint authentication device comprising the photoelectric conversion element according to claim 8.

11. A vein authentication device comprising the photoelectric conversion element according to claim 8.

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