Photoelectric conversion element and photosensor

Abstract

The problem addressed by this invention is to provide a photelectric conversion element and a photosensor having a wide band of wavelengths that can be detected with high sensitivity in the long-wavelength range.　The present invention provides a photoelectric conversion element (10) having an anode (12), a cathode (17), and an active layer (19) present between the anode (12) and the cathode (17), wherein the active layer (19) has at least a first layer (14) containing either a p-type semiconductor material or an n-type semiconductor material and a second layer (15) containing a semiconductor material of a different type from the semiconductor material contained in the first layer (14), and the maximum optical absorption wavelength (λmax) of the active layer (19) exceeds 1000 nm.　The present invention further provides a photoelectric conversion element (10) wherein the optical absorption terminal wavelength (λth) of the active layer (19) is 1200 nm or higher.　The present invention further provides a photoelectric conversion element (10) wherein the p-type semiconductor material or the n-type semiconductor material contained in the first layer (14) has an energy band gap of less than 1 eV.

Description

Photoelectric conversion element and optical sensor

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

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

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

[0004] For example, Non-Patent Documents 1 and 2 disclose organic photodetectors (OPDs) that perform photoelectric conversion of light in the vicinity of the visible light region.

[0005] Zeyu He et al., Reverse-distribution phase featured gradient heterojunction: A universal strategy to realize high-performance near-infrared organic photodetectors for real-time arterial monitoring, Nano Energy 114 (2023)108673Ying Zhang et al., Graded bulk-heterojunction enables 17% binary organic solar cells via nonhalogenated open air coating, NATURE COMMUNICATIONS (2021) 12:4815

[0006] However, in previous reports, knowledge regarding photoelectric conversion elements for light in the long wavelength band was limited. The present disclosure has been made in view of the above, and relates to providing a photoelectric conversion element and an optical sensor that can detect light in the long wavelength band with high sensitivity and have a wide wavelength band.

[0007] Specific means for solving the above problems include the following aspects. <1> A photoelectric conversion element comprising an anode, a cathode, and an active layer located between the anode and the cathode, wherein the active layer comprises at least a first layer containing either a p-type semiconductor material or an n-type semiconductor material, and a second layer containing a semiconductor material of a type different from that of the semiconductor material contained in the first layer, and wherein the active layer has a maximum light absorption wavelength (λmax) of greater than 1000 nm. <2> The photoelectric conversion element according to <1>, wherein the active layer has a light absorption end wavelength (λth) of 1200 nm or greater. <3> The photoelectric conversion element according to <1> or <2>, wherein the p-type semiconductor material or the n-type semiconductor material contained in the first layer has an energy band gap of less than 1 eV. <4> The photoelectric conversion element according to any one of <1> to <3>, wherein the semiconductor material contained in the first layer is an n-type semiconductor material. <5> The photoelectric conversion element according to any one of <1> to <4>, wherein the semiconductor material contained in the first layer is an n-type semiconductor material having a LUMO energy of −4.2 eV or less. <6> The photoelectric conversion element according to any one of <1> to <5>, wherein the semiconductor material contained in the first layer is an n-type semiconductor material having a HOMO energy of −5.0 eV or less. <7> The photoelectric conversion element according to any one of <1> to <6>, wherein the semiconductor material contained in the first layer is an n-type semiconductor material, and the n-type semiconductor material is a compound represented by the following formula (1):

[0008]

[0009] In formula (1), D is an electron-donating divalent group, and the monovalent side chain R Ｄ１ L1 is a divalent aromatic group and has at least one monovalent side chain R Ｌ１The aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, and R Ｄ１ and R Ｌ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; L2 is a divalent aromatic group; m is an integer of 1 to 4, n is an integer of 0 to 4, and A1 and A2 are each independently a group represented by the following formula (A-1).

[0010]

[0011] In formula (A-1), Ar represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent, and the carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a fused ring, and when the carbocyclic ring or the heterocyclic ring has a plurality of substituents, the plurality of substituents may be the same or different. <8> The photoelectric conversion element according to <7>, wherein n is an integer of 1 to 4. <9> The photoelectric conversion element according to any one of <1> to <8>, wherein the first layer is in contact with a second layer containing a p-type semiconductor material and an n-type semiconductor material. <10> The photoelectric conversion element according to any one of <1> to <9>, wherein the second layer contains a p-type semiconductor material, and the p-type semiconductor material is a hole transport material. <11> The photoelectric conversion element according to any one of <1> to <10>, wherein the second layer contains a p-type semiconductor material, and the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4):

[0012]

[0013] In formula (3), Ar ３ and Ar ４ each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulas (Z-1) to (Z-7):

[0014]

[0015] In formulae (Z-1) to (Z-7), R each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amide group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different from each other, and in formula (4), Ar ５ represents a divalent aromatic heterocyclic group. <12> The photoelectric conversion element according to any one of <1> to <11>, which is a light detection element. <13> An optical sensor including the photoelectric conversion element according to <12>.

[0016] According to the present disclosure, a photoelectric conversion element and an optical sensor are provided that are capable of detecting light with high sensitivity over a wide wavelength range in the long wavelength range.

[0017] FIG. 1 is a diagram schematically illustrating an example of the configuration of a photoelectric conversion element.

[0018] An embodiment of the present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiment. In the following disclosure, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0019] The photoelectric conversion element of the present disclosure will be described below with reference to the drawings. Note that the drawings merely show the shape, size, and arrangement of the components in a schematic manner to the extent that the invention can be understood. The present disclosure is not limited by the following description, and each component can be modified as appropriate within the scope of the gist of the present disclosure. Furthermore, the configuration of the present disclosure is not necessarily manufactured or used in the arrangement shown in the drawings.

[0020] In the present disclosure, when a numerical range is indicated using "to", the numerical values ​​before and after "to" are included as the lower and upper limits, respectively. In the present disclosure, when a numerical range is described in stages, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another staged numerical range. Furthermore, in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, when multiple substances corresponding to each component are present in the composition, the content of each component refers to the total content of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, when multiple elements are listed using "or", this does not exclude the combination of multiple elements unless a technical contradiction occurs, unless otherwise specified. In the present disclosure, when an element is described in the singular, this does not exclude the presence of multiple elements unless a technical contradiction occurs, unless otherwise specified. In the present disclosure, multiple exemplary embodiments described separately may be combined with each other to form a new embodiment, unless mutually contradictory.

[0021] The following describes commonly used terms in this disclosure. In the description of this disclosure, the following descriptions apply unless otherwise specified.

[0022] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0023] The term "π-conjugated system" refers to a system in which π electrons are delocalized among multiple bonds.

[0024] The term "polymer compound" refers to a compound having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1×10 ３ 1x10 or more ８ The total amount of structural units contained in the polymer compound is 100 mol %.

[0025] The term "structural unit" refers to a residue derived from a raw material compound (monomer), of which one or more are present in a compound or polymer compound.

[0026] The "hydrogen atom" may be a protist atom or a deuterium atom.

[0027] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0028] The embodiment in which "may have a substituent" includes both a case in which all hydrogen atoms constituting the compound or group are unsubstituted, and a case in which one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0029] Examples of the "substituent" include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an alkyloxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. In this specification, when referring to the number of carbon atoms, the number of carbon atoms does not usually include the number of carbon atoms of the substituent.

[0030] In this specification, unless otherwise specified, an "alkyl group" may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkyl group, not including the number of carbon atoms of substituents, is usually preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. The number of carbon atoms in a branched or cyclic alkyl group, not including the number of carbon atoms of substituents, is usually preferably 3 to 50, more preferably 3 to 30, and even more preferably 4 to 20.

[0031] Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, a 2-ethylbutyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a cyclohexylmethyl group, a cyclohexylethyl group, an n-octyl group, a 2-ethylhexyl group, a 3-n-propylheptyl group, an adamantyl group, an n-decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-n-hexyl-decyl group, an n-dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group.

[0032] 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.

[0033] 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.

[0034] The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group, not including the number of carbon atoms of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0035] 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.

[0036] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0037] The term "aromatic carbocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent. The aromatic carbocyclic group may further have a substituent. The term "aromatic carbocyclic ring" also includes a structure in which two or more carbocyclic rings (aromatic rings) are connected together via, for example, a group (substituent) containing a heteroatom.

[0038] The term "aryl group" refers to a monovalent aromatic carbocyclic group, which is an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring from an aromatic hydrocarbon which may have a substituent.

[0039] The aryl group may have a substituent. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and groups in which a hydrogen atom in these groups has been substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0040] The "alkyloxy group" (alkoxy group) may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkyloxy group, not including the number of carbon atoms of the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkyloxy group, not including the number of carbon atoms of the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0041] 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.

[0042] The cycloalkyl group in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group, not including the number of carbon atoms of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0043] Examples of the cycloalkyloxy group include unsubstituted cycloalkyloxy groups such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group, as well as groups in which a hydrogen atom in these groups has been substituted with a fluorine atom or an alkyl group.

[0044] The number of carbon atoms in the "aryloxy group" is usually preferably 6 to 60, more preferably 6 to 48, not including the number of carbon atoms of the substituents.

[0045] The aryloxy group may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and groups in which a hydrogen atom in these groups has been substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0046] The "alkylthio group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkylthio group, not including the number of carbon atoms of substituents, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in a branched or cyclic alkylthio group, not including the number of carbon atoms of substituents, is usually preferably 3 to 40, more preferably 4 to 10.

[0047] 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.

[0048] The cycloalkyl group in the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms in the cycloalkylthio group, not including the number of carbon atoms of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0049] Examples of the optionally substituted cycloalkylthio group include a cyclohexylthio group.

[0050] The number of carbon atoms of the "arylthio group" is usually preferably 6 to 60, more preferably 6 to 48, not including the number of carbon atoms of the substituents.

[0051] 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.

[0052] The term "heterocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an optionally substituted heterocyclic compound.

[0053] The heterocyclic group may further have a substituent. The number of carbon atoms of the heterocyclic group is usually preferably 2 to 30, more preferably 2 to 6, not including the number of carbon atoms of the substituent.

[0054] Examples of the substituent that the heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group. The heterocyclic group includes an "aromatic heterocyclic group."

[0055] The term "aromatic heterocyclic group" refers to an atomic group remaining after removing any number of hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an aromatic heterocyclic compound which may have a substituent. The aromatic heterocyclic group may further have a substituent.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] The number of carbon atoms in the monovalent heterocyclic group is usually preferably 2 to 60, more preferably 4 to 20, not including the number of carbon atoms in the substituent.

[0060] 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.

[0061] The term "substituted amino group" refers to an amino group having a substituent. Examples of the substituent on the amino group include an alkyl group, an aryl group, and a monovalent heterocyclic group, with an alkyl group, an aryl group, or a monovalent heterocyclic group being preferred. The number of carbon atoms in the substituted amino group is usually preferably 2 to 30.

[0062] 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.

[0063] The "acyl group" may have a substituent. The number of carbon atoms in the acyl group, not including the number of carbon atoms of the substituent, is usually preferably 2 to 20, and more preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

[0064] 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.

[0065] The imine residue generally preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the following structural formula: In the following structural formula, Me represents a methyl group.

[0066]

[0067] The term "amide group" refers to the atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an amide. The number of carbon atoms in the amide group is usually preferably 1 to 20, and more preferably 1 to 18. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyromido group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyromido group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

[0068] 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 an acid imide group is usually preferably 4 to 20. Specific examples of acid imide groups include groups represented by the following structural formula: In the structural formula, Me represents a methyl group.

[0069]

[0070] The term "substituted carbonyl group" refers to a group represented by -(C=O)-R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0071] The "substituted oxycarbonyl group" is a group represented by -(C=O)-O-R Ｘ or —O—(C═O)—R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0072] The "substituted sulfonyl group" is a group represented by -SO ２ -R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0073] The term "substituted oxysulfonyl group" refers to a group selected from the group consisting of -(SO ２ )-O-R Ｘ or -O-(SO ２ )-R Ｘ where R Ｘ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0074] The number of carbon atoms of the substituted oxycarbonyl group is usually preferably 2 to 60, more preferably 2 to 48, not including the number of carbon atoms of the substituent.

[0075] 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.

[0076] The "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms in a linear alkenyl group, not including the number of carbon atoms of substituents, is usually preferably 2 to 30, more preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkenyl group, not including the number of carbon atoms of substituents, is usually preferably 3 to 30, more preferably 4 to 20.

[0077] The alkenyl group may have a substituent. Specific examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 7-octenyl, and groups in which hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, or fluorine atoms.

[0078] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group, not including the number of carbon atoms of the substituent, is usually preferably 3 to 30, and more preferably 12 to 19.

[0079] 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.

[0080] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0081] The "alkynyl group" may be any of linear, branched, and cyclic. The number of carbon atoms in a linear alkynyl group, not including the number of carbon atoms of substituents, is usually preferably 2 to 20, more preferably 3 to 20. The number of carbon atoms in a branched or cyclic alkynyl group, not including the number of carbon atoms of substituents, is usually preferably 4 to 30, more preferably 4 to 20.

[0082] The alkynyl group may have a substituent. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and groups in which a hydrogen atom in these groups has been substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0083] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group, not including the number of carbon atoms of the substituent, is usually preferably 4 to 30, and more preferably 12 to 19.

[0084] 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.

[0085] Examples of the substituted cycloalkynyl group include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0086] The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group, not including the number of carbon atoms in the substituent, is usually preferably 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0087] The symbol "*" that may be attached to a chemical formula represents a bond. A dotted line in a chemical formula also represents a bond. When a chemical formula contains two symbols "*" and two dotted lines, there is no particular limitation as to which of the two units to which the bond is attached.

[0088] "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.

[0089] The ink may be a solution or a dispersion such as an emulsion or suspension.

[0090] 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.

[0091] "External quantum efficiency" is also called EQE (External Quantum Efficiency), and refers to a value expressed as a ratio (%) of the number of electrons that can be extracted outside the photoelectric conversion element out of the number of electrons generated relative to the number of photons irradiated onto the photoelectric conversion element.

[0092] <Photoelectric Conversion Element> The photoelectric conversion element of the present disclosure comprises an anode, a cathode, and an active layer present between the anode and the cathode, wherein the active layer comprises at least a first layer containing either a p-type semiconductor material or an n-type semiconductor material, and a second layer containing a semiconductor material of a type different from the semiconductor material contained in the first layer, and wherein the maximum light absorption wavelength (λmax) of the active layer exceeds 1000 nm.

[0093] The photoelectric conversion element of the present disclosure is a photoelectric conversion element capable of detecting light with high sensitivity over a wide wavelength range in the long wavelength band. The function of the photoelectric conversion element of the present disclosure is not clear, but is presumed to be as follows. The active layer of the present disclosure has a planar heterojunction structure (PHJ structure) having at least a first layer and a second layer. The first layer contains either a p-type semiconductor material or an n-type semiconductor material. That is, the first layer is a single film (also referred to as a single layer) containing only either a p-type semiconductor material or an n-type semiconductor material. On the other hand, the second layer contains a semiconductor material of a different type from the semiconductor material contained in the first layer. That is, the second layer is a single film containing only either a p-type semiconductor material or an n-type semiconductor material, or a mixed film (also referred to as a mixed layer) containing both a p-type semiconductor material and an n-type semiconductor material. Here, if the molecules of the semiconductor material in the active layer are regularly stacked, the semiconductor material can absorb light of longer wavelengths and further broaden the wavelength range in which it can absorb light with high absorbance. Therefore, when a single film is present in the active layer, such as the first layer in the active layer of the photoelectric conversion element of the present disclosure, the semiconductor material can absorb light of longer wavelengths, and the wavelength band that can be absorbed with high absorbance is wider. On the other hand, in a mixed film containing both p-type and n-type semiconductor materials, the p-type and n-type semiconductor materials are mixed. That is, in the mixed film, the molecules of the p-type semiconductor material and the molecules of the n-type semiconductor material have an irregular intertwined structure, and regular overlapping between the molecules is inhibited. Therefore, in the mixed film, the semiconductor material cannot absorb light of longer wavelengths, and the wavelength band that can be absorbed with high absorbance is narrowed.

[0094] Furthermore, the maximum light absorption wavelength (λmax) of the active layer in the photoelectric conversion element of the present disclosure exceeds 1000 nm, that is, the active layer can absorb light in the long wavelength band around 1000 nm.

[0095] The photoelectric conversion element of the present disclosure also includes a photoelectric conversion element capable of detecting a wide wavelength range with high sensitivity in the short wavelength range. The active layer in the photoelectric conversion element capable of detecting a wide wavelength range with high sensitivity in the short wavelength range has a PHJ structure having at least the first and second layers as described above. At the interface between the first and second layers, the p-type semiconductor material and the n-type semiconductor material overlap, thereby broadening the absorption wavelength range in the short wavelength range.

[0096] For the above reasons, the photoelectric conversion element of the present disclosure is a photoelectric conversion element that can detect light in a wide wavelength range with high sensitivity in the long wavelength range. Note that the present disclosure is not limited to the above-mentioned estimated mechanism.

[0097] Here, an example of a configuration that the photoelectric conversion element of the present disclosure can take will be described. Fig. 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure. Note that Fig. 1 is a diagram for explanation by example and does not limit the embodiment of the present disclosure.

[0098] As shown in Fig. 1, the photoelectric conversion element 10 is preferably provided on a support substrate 11. The photoelectric conversion element 10 preferably 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 19 provided in contact with the hole transport layer 13, an electron transport layer 16 provided in contact with the active layer 19, and a cathode 17 provided in contact with the electron transport layer 16. A sealing member 18 is preferably further provided in contact with the cathode 17. The active layer 19 preferably includes a first layer 14 and a second layer 15, and the first layer 14 is preferably provided in contact with the hole transport layer 13, and the second layer 15 is preferably provided in contact with the electron transport layer 16.

[0099] The first layer 14 may be provided so as to be in contact with the electron transport layer 16 , and the second layer 15 may be provided so as to be in contact with the hole transport layer 13 .

[0100] Another example of a photoelectric conversion element includes a cathode provided in contact with a support substrate, an electron transport layer provided in contact with the cathode, an active layer provided in contact with the electron transport layer, a hole transport layer provided in contact with the active layer, and an anode provided in contact with the hole transport layer. In this example, a sealing member is further provided in contact with the anode. The active layer has at least a first layer and a second layer, and the first layer may be provided in contact with either the electron transport layer or the hole transport layer, and the second layer may be provided in contact with either the electron transport layer or the hole transport layer.

[0101] Another example of a photoelectric conversion element includes an anode provided in contact with a support substrate, an active layer provided in contact with the anode, an electron transport layer provided in contact with the active layer, and a cathode provided in contact with the electron transport layer. The active layer has at least a first layer and a second layer, and the first layer may be provided in contact with either the anode or the electron transport layer, and the second layer may be provided in contact with either the anode or the electron transport layer.

[0102] Components that can be included in the photoelectric conversion element of the present disclosure will be specifically described below.

[0103] <Active Layer> The active layer of the present disclosure is located between an anode and a cathode, which will be described later. The active layer of the present disclosure may be located in the order of the anode, active layer, and cathode in the vertical direction, or may be located in the order of the anode, hole transport layer, active layer, electron transport layer, and cathode in the vertical direction, as shown in Figure 1 or Figure 2.

[0104] (Maximum Light Absorption Wavelength (λmax) of Active Layer) The maximum light absorption wavelength (λmax) of the active layer exceeds 1000 nm. The photoelectric conversion element of the present disclosure is more likely to perform photoelectric conversion in light of a longer wavelength band than conventional elements. From the viewpoint of absorbing long-wavelength light, the maximum light absorption wavelength of the active layer is preferably 1059 nm or more, more preferably 1100 nm or more, even more preferably 1150 nm or more, even more preferably 1200 nm or more, even more preferably 1250 nm or more, even more preferably 1300 nm or more, and particularly preferably 1350 nm or more. The upper limit of the maximum light absorption wavelength of the active layer is not particularly limited, and may be, for example, 2500 nm or less, 2300 nm or less, 2000 nm or less, or 1800 nm or less. In one embodiment of the present disclosure, the maximum light absorption wavelength of the active layer is preferably 1059 nm to 1800 nm.

[0105] The maximum light absorption wavelength of the active layer is expressed as the wavelength value of the absorption peak wavelength. In the present disclosure, the maximum light absorption wavelength of the active layer is specifically expressed by a value determined by the following method.

[0106] The measurement sample was prepared as follows.

[0107] - Ink Preparation - A p-type semiconductor material (polymer compound) is added to a 1,2-dimethylbenzene solvent at 60°C for 8 hours to give a concentration of 1% by mass relative to the total mass of the ink, and the resulting mixture is filtered using a filter to obtain an ink containing a p-type semiconductor material. An n-type semiconductor material (polymer compound) is added to a toluene solvent at 60°C for 8 hours to give a concentration of 1% by mass relative to the total mass of the ink, and the resulting mixture is filtered using a filter to obtain an ink containing an n-type semiconductor material. A chloroform and chloronaphthalene mixed solvent (98:2 volume ratio) is added to an n-type semiconductor material at 1% by mass relative to the total mass of the ink, and the p-type semiconductor material is added to a chloroform and chloronaphthalene mixed solvent (98:2 volume ratio) at room temperature for 8 hours to give a concentration of 1% by mass relative to the total mass of the ink, and the resulting mixture is filtered using a filter to obtain an ink containing an n-type semiconductor material and a p-type semiconductor material.

[0108] - Preparation of active layer - An ink containing an n-type semiconductor material and / or a p-type semiconductor material is applied by spin coating onto a cleaned glass substrate to form a coating film, which is then heat-treated and dried for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heat-treated for 10 minutes at 100°C on a hot plate in the atmosphere (post-bake step) to form a first layer. Next, an ink containing an n-type semiconductor material and / or a p-type semiconductor material is applied by spin coating onto the first layer to form a coating film, which is then heat-treated and dried for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heat-treated for 10 minutes at 100°C on a hot plate in the atmosphere (post-bake step) to form a second layer, thereby preparing a PHJ film (active layer).

[0109] - Measurement - The light absorption wavelength is measured using a spectrophotometer that operates in the ultraviolet, visible, and near-infrared wavelength regions (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian).

[0110] The absorption spectrum of the active layer is shown with the absorbance of the active layer on the vertical axis and the wavelength on the horizontal axis. It is desirable to adjust the film thickness of the active layer so that the absorbance of the largest absorption peak is about 0.4 to 2.

[0111] Among the absorption peaks of the absorption spectrum measured in the wavelength range of 300 nm to 2000 nm, the absorption peak point (maximum value) closest to the longest wavelength is taken as the value of the maximum light absorption wavelength.

[0112] (Photoabsorption terminal wavelength (λth) of active layer) The photoabsorption terminal wavelength (λth) of the active layer is preferably 1200 nm or more. The photoelectric conversion element of the present disclosure is more likely to perform photoelectric conversion in light of a longer wavelength band than conventional elements. From the viewpoint of absorbing long-wavelength light, the photoabsorption terminal wavelength of the active layer is preferably 1200 nm or more, more preferably 1250 nm or more, even more preferably 1300 nm or more, even more preferably 1350 nm or more, even more preferably 1400 nm or more, even more preferably 1450 nm or more, and particularly preferably 1500 nm or more. The upper limit of the photoabsorption terminal wavelength of the active layer is not particularly limited, and may be, for example, 3000 nm or less, 2500 nm or less, 2300 nm or less, or 2100 nm or less. In one embodiment of the present disclosure, the photoabsorption terminal wavelength of the active layer is preferably 1200 nm to 3000 nm.

[0113] The optical absorption end wavelength of the active layer is expressed as the wavelength value of the end of the optical absorption wavelength on the long wavelength side. In this disclosure, the numerical value of the optical absorption end wavelength is specifically expressed by a value calculated by the following method.

[0114] The measurement sample can be prepared in the same manner as the ink preparation and active layer preparation methods used in measuring the maximum light absorption wavelength of the active layer.

[0115] - Measurement - The light absorption wavelength is measured using a spectrophotometer that operates in the ultraviolet, visible, and near-infrared wavelength regions (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian).

[0116] First, the absorption spectrum of the substrate used for measurement is measured. A quartz substrate, a glass substrate, or the like is used as the substrate. Next, an active layer is formed on the substrate as described above. Thereafter, the absorption spectrum of the laminate of the active layer and the substrate is obtained. The difference between the absorption spectrum of the laminate of the active layer and the substrate and the absorption spectrum of the substrate is obtained as the absorption spectrum of the active layer.

[0117] The absorption spectrum of the active layer is shown with the absorbance of the active layer on the vertical axis and the wavelength on the horizontal axis. It is desirable to adjust the film thickness of the active layer so that the absorbance of the largest absorption peak is about 0.4 to 2.

[0118] The optical absorption end wavelength can be determined from the intersection of the first reference line and the second reference line shown below.

[0119] - First Reference Line - The absorbance at the absorption peak point (maximum value) closest to the longest wavelength in the entire absorption waveform (absorption spectrum) is set to 100%.

[0120] Of the two intersections where the absorption waveform intersects with a line parallel to the horizontal axis (wavelength axis) showing 50% absorbance of the absorption peak point, the intersection located closer to the longer wavelength side than the absorption peak point is defined as the first point.

[0121] Of the two intersections between the absorption waveform and a line parallel to the wavelength axis showing an absorbance of 44% of the absorption peak point, the intersection located closer to the longer wavelength side than the absorption peak point is designated as the second point. The line connecting the first point and the second point is designated as the first reference line.

[0122] - Second Reference Line - The absorbance at the absorption peak point (maximum value) closest to the longest wavelength in the entire absorption waveform is set to 100%.

[0123] Of the two intersections between the absorption waveform and a line parallel to the wavelength axis showing 20% ​​absorbance of the absorption peak point, the wavelength of the intersection point that is longer than the absorption peak point is taken as the reference point, and a point on the absorption waveform that is 200 nm longer than the reference point wavelength is taken as the third point. Also, a point on the absorption waveform that is 250 nm longer than the reference point wavelength is taken as the fourth point. The line connecting the third and fourth points is taken as the second reference line.

[0124] The wavelength value at the intersection of the first reference line and the second reference line is defined as the optical absorption terminal wavelength.

[0125] [First Layer] The active layer of the present disclosure has at least a first layer and a second layer. The first layer contains either a p-type semiconductor material or an n-type semiconductor material. That is, the first layer is a single film. From the viewpoint of facilitating photoelectric conversion, it is preferable that the first layer be in contact with the second layer, more preferably that at least a portion of the first layer be in contact with at least a portion of the second layer, and even more preferably that the first layer and the second layer are stacked. It is even more preferable that the first layer be in contact with the second layer containing a p-type semiconductor material and an n-type semiconductor material.

[0126] (Energy Band Gap (Eg)) From the viewpoint of absorbing light with a long wavelength, the p-type semiconductor material or n-type semiconductor material contained in the first layer preferably has an energy band gap (Eg) of less than 1 eV, and more preferably less than 1.0 eV.

[0127] The energy band gap (Eg) is calculated using the optical absorption end wavelength (λth) of the semiconductor material contained in the active layer according to the following formula. The details of the measurement method are as described in the Examples. Energy band gap (Eg) = hc / optical absorption end wavelength (Planck's constant h = 6.626 × 10 -34 Js, speed of light c=3×10 8 m / s)

[0128] When the energy band gap of the p-type semiconductor material or the n-type semiconductor material contained in the first layer is less than 1 eV, the photoelectric conversion element of the present disclosure is more likely to perform photoelectric conversion at longer wavelengths.

[0129] From the viewpoint of absorbing long-wavelength light, the energy band gap of the p-type semiconductor material or n-type semiconductor material contained in the first layer is more preferably 1.0 eV or less, even more preferably 0.9 eV or less, and particularly preferably 0.8 eV or less. The lower limit of the energy band gap of the p-type semiconductor material or n-type semiconductor material contained in the first layer is not particularly limited, but is, for example, 0.3 eV or 0.4 eV. In one embodiment of the present disclosure, the energy band gap of the p-type semiconductor material or n-type semiconductor material contained in the first layer is preferably 1.0 eV to 0.4 eV.

[0130] (n-Type Semiconductor Material) From the viewpoint of adjusting the light absorption wavelength, the semiconductor material contained in the first layer is preferably an n-type semiconductor material. The semiconductor material contained in the first layer is preferably a low-molecular-weight n-type semiconductor material, more preferably an n-type semiconductor material having a weight-average molecular weight of 100,000 to 300, even more preferably an n-type semiconductor material having a weight-average molecular weight of 10,000 to 400, and particularly preferably an n-type semiconductor material having a weight-average molecular weight of 5,000 to 500.

[0131] From the viewpoint of improving the photoelectric conversion rate, the LUMO energy of the n-type semiconductor material is preferably −4.2 eV or less, more preferably −4.3 eV or less, even more preferably −4.4 eV or less, and particularly preferably −4.5 eV or less. The lower limit of the LUMO energy of the n-type semiconductor material is not particularly limited, but is, for example, −5.0 eV, −4.9 eV, or −4.8 eV. In one embodiment of the present disclosure, the LUMO energy of the n-type semiconductor material is preferably −4.2 eV to −4.7 eV.

[0132] From the viewpoint of improving the photoelectric conversion efficiency, the HOMO energy of the n-type semiconductor material is preferably -5.0 eV or less, more preferably -5.1 eV or less, even more preferably -5.2 eV or less, and particularly preferably -5.3 eV or less. The lower limit of the HOMO energy of the n-type semiconductor material is not particularly limited, but is, for example, -5.9 eV, -5.8 eV, or -5.7 eV. In one embodiment of the present disclosure, the HOMO energy of the n-type semiconductor material is preferably -5.0 eV to -5.6 eV.

[0133] In the present disclosure, the HOMO energy and LUMO energy can be calculated by any suitable conventionally known computational science method. Specifically, they are calculated using the following formula: LUMO energy = energy band gap (Eg) - HOMO energy Band gap (Eg) = hc / light absorption end wavelength

[0134] {Compound as n-type semiconductor material} The n-type semiconductor material is preferably a compound represented by the following formula (1).

[0135]

[0136] In formula (1), D is an electron-donating divalent group, and the monovalent side chain R Ｄ１ L1 is a divalent aromatic group and has at least one monovalent side chain R Ｌ１ The aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, and R Ｄ１ and R Ｌ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group; L2 is a divalent aromatic group; m is an integer of 1 to 4, n is an integer of 0 to 4, and A1 and A2 are each independently a group represented by the following formula (A-1).

[0137]

[0138] In formula (A-1), Ar represents a carbocycle which may have a substituent, or a heterocycle which may have a substituent, and the carbocycle and the heterocycle are each independently a monocycle or a fused ring, and when the carbocycle or the heterocycle has a plurality of substituents, the plurality of substituents may be the same or different.

[0139] [D; Core] - Aromatic Group - In formula (1), D is an electron-donating divalent group. D is preferably a divalent aromatic group, and more preferably has a monocyclic or fused ring main skeleton. The aromatic group may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and an aromatic heterocyclic group is preferred from the viewpoint of absorbing long wavelength light. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, and more preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a nitrogen atom, and an oxygen atom.

[0140] The main skeleton of the monocyclic or fused ring constituting the aromatic group may have at least one of sp3 carbon and sp3 silicon. The main skeleton of the monocyclic or fused ring constituting the aromatic group in D preferably has sp3 carbon or sp3 silicon.

[0141] D is a monovalent side chain R bonded to the sp3 carbon or the sp3 silicon. Ｄ１ D preferably has at least one monovalent side chain R bonded to the sp3 carbon or sp3 silicon. Ｄ１ As described above, it is preferable that the main skeleton of the monocyclic or fused ring constituting the aromatic group in D has at least one of an sp3 carbon and an sp3 silicon, and D has a monovalent side chain R Ｄ１ As a result, the molecule of the compound that is an n-type semiconductor material has at least one of the side chains R Ｄ１Since the compound represented by formula (1) of the present disclosure has a structure in which the groups protrude in the vertical direction, the compound is less likely to undergo H-aggregation and more likely to undergo J-aggregation in the formed thin film.

[0142] -Side chain R Ｄ１ - Side chain R in D Ｄ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0143] Side chain R in D Ｄ１ The specific structure of the side chain R in D is not particularly limited. Ｄ１ are each independently preferably an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted monovalent heterocyclic group, more preferably an optionally substituted alkyl group or an optionally substituted aryl group, and even more preferably an alkyl group.

[0144] —Chemical Structure of D— In view of the ease with which the compound absorbs light of long wavelengths, D in the formula (1) is preferably a group represented by the following formula (D-1) or (D-2): In the following formulas (D-1) and (D-2), the symbol “*” represents (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0145]

[0146] In formula (D-1) and formula (D-2), X is any of the groups represented by the following formulas (X-1) to (X-6).

[0147]

[0148] In formulas (X-1) to (X-6), R Ｄ２ The definitions of each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0149] In each of formulas (X-1) to (X-6), R Ｄ２If there are two R Ｄ２ may be the same or different. From the viewpoint that the compound easily absorbs light of a long wavelength, X is preferably any of the groups represented by formula (X-1) to formula (X-4), and more preferably any of the groups represented by formula (X-1), formula (X-3), or formula (X-4). In formulas (X-1) to (X-6), R Ｄ２ is preferably a hydrogen atom or the above-mentioned R Ｄ１ This is the same as the preferred embodiment of

[0150] In formula (D-2), Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ Either one of them may not be present.

[0151] Ar １ and Ar ２ The aromatic heterocycle that can constitute the above ring includes not only a single ring and a fused ring in which the heterocycle itself exhibits aromaticity, but also a ring in which an aromatic ring is fused to a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0152] Ar １ and Ar ２ The aromatic heterocycles that can constitute the above may each be a single ring or a fused ring. When the aromatic heterocycle is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the rings may be fused rings having aromaticity. When these rings have multiple substituents, these substituents may be the same or different.

[0153] Ar １ and Ar ２Specific examples of aromatic carbocyclic rings that can constitute the above ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and are preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0154] Ar １ and Ar ２ Specific examples of aromatic heterocycles that can constitute the above include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0155] -Examples of D- Examples of formula (D-1) include groups represented by the following formulas (d-1-1) to (d-1-7). Examples of formula (D-2) include groups represented by the following formulas (d-2-1) to (d-2-10). In formulas (d-1-1) to (d-1-7) and formulas (d-2-1) to (d-2-10), R Ｄ２ The definitions of each independently are the same as those of R Ｄ２ In the following formulas (d-2-1) to (d-2-10), U is each independently S, SiR Ｄ２ ２ , Se, NR Ｄ２ or O. U is preferably S. In the following formulas (d-1-1) to (d-1-7) and (d-2-1) to (d-2-10), the symbol "*" represents (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0156] From the viewpoint that the compound easily absorbs light of a long wavelength, D is preferably a group represented by formula (d-1-1), formula (d-1-3) to formula (d-1-7), or formula (d-2-1) to formula (d-2-10), more preferably a group represented by formula (d-1-1) or formula (d-1-3) to formula (d-1-7), and even more preferably a group represented by formula (d-1-1), formula (d-1-3), or formula (d-1-4).

[0157]

[0158]

[0159] Specific examples of D include groups represented by the following formulae. In each formula, the symbol "*" indicates (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0160]

[0161] [(L1) ｍ (L1) in formula (1) ｍ In the formula (1), when m is 2 or more, the chemical structure of each of the L1s present in the formula (1) is independently defined. In other words, the following description of L1 is a description of each of the L1s independently.

[0162] -Aromatic Group- In formula (1), L1 is a divalent aromatic group. The aromatic group in L1 preferably has a monocyclic or fused ring main skeleton. The aromatic group in L1 may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and is preferably an aromatic heterocyclic group from the viewpoint of absorbing long wavelength light. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, and more preferably at least one selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.

[0163] The main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 may or may not have sp3 carbon or sp3 silicon. The main skeleton of the monocyclic or fused ring constituting the aromatic group in L1 may or may not have sp2 carbon or sp2 silicon.

[0164] -Non-covalent interaction- The aromatic group in L1 preferably has an element capable of non-covalent interaction with an element in an adjacent unit. In the present disclosure, A1, L1, L2, or D is each a structural unit, and the structural unit is referred to as a unit. The adjacent units may be adjacent units on both sides, or one of the adjacent units on both sides. Examples of adjacent units include A1 and L1, L1 and D, and (L1) ｍ When m is 2 or more, adjacent L1s can be mentioned.

[0165] The element possessed by the aromatic group in L1 and capable of non-covalently interacting with an element in an adjacent unit is preferably at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, more preferably at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, and a nitrogen atom, and even more preferably at least one of a sulfur atom and an oxygen atom.

[0166] The aromatic group in L1 preferably has an element capable of non-covalently interacting with an element in an adjacent unit, selected from the group consisting of a sulfur atom-oxygen atom, a sulfur atom-fluorine atom, a sulfur atom-nitrogen atom, a selenium atom-oxygen atom, a selenium atom-nitrogen atom, a nitrogen atom-oxygen atom, and an oxygen atom-phosphorus atom.

[0167] Similarly, the unit adjacent to L1 preferably has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom. The unit adjacent to L1 preferably has an element capable of non-covalently interacting with the aromatic group in L1, selected from the group consisting of a sulfur atom-oxygen atom, a sulfur atom-fluorine atom, a sulfur atom-nitrogen atom, a selenium atom-oxygen atom, a selenium atom-nitrogen atom, a nitrogen atom-oxygen atom, and an oxygen atom-phosphorus atom.

[0168] From the viewpoint of enabling non-covalent interactions, when the aromatic group in L1 has a sulfur atom, the unit adjacent to L1 preferably has at least one selected from the group consisting of an oxygen atom, a fluorine atom, and a nitrogen atom. When the aromatic group in L1 has an oxygen atom, the unit adjacent to L1 preferably has at least one selected from the group consisting of a sulfur atom, a selenium atom, a nitrogen atom, and a phosphorus atom. When the aromatic group in L1 has a fluorine atom, the unit adjacent to L1 preferably has a sulfur atom. When the aromatic group in L1 has a nitrogen atom, the unit adjacent to L1 preferably has at least one selected from the group consisting of a sulfur atom, a selenium atom, and an oxygen atom. When the aromatic group in L1 has a selenium atom, the unit adjacent to L1 preferably has at least one of an oxygen atom and a nitrogen atom. When the aromatic group in L1 has a phosphorus atom, the unit adjacent to L1 preferably has an oxygen atom.

[0169] At least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom may be contained in the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1, or may be contained in a side chain bonded to the main skeleton of the monocyclic or fused ring constituting the aromatic group in L1, and the side chain R Ｌ１ The non-covalent interaction may be formed between the main skeleton of the single ring or fused ring constituting the aromatic group in L1 and a side chain bonded to the main skeleton of the unit adjacent to L1, and the side chain R bonded to the main skeleton of the single ring or fused ring constituting the aromatic group in L1 may beＬ１ and the main skeleton of an adjacent unit to L1, or may be formed by side chains bonded to the main skeleton of a single ring or fused ring constituting the aromatic group in L1.

[0170] As described above, when the aromatic group in L1 contains an element capable of non-covalently interacting with an element in an adjacent unit, a non-covalent bridge is formed between the element in L1 and the unit (A1, L1, or D) adjacent to L1. In other words, the planarity of the main skeleton (i.e., the π plane) of the single ring or fused ring constituting the aromatic group in L1 is likely to be maintained in the formed thin film.

[0171] -Side chain R Ｌ１ - Side chain R in L1 Ｌ１ each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0172] From the viewpoint that the compound is likely to absorb light of a long wavelength, the side chain R Ｌ１are each independently preferably an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, a substituted amino group which may have a substituent, an alkyl group which may have a substituent, or a halogen atom, more preferably an alkyloxy group which may have a substituent or a halogen atom, and even more preferably an alkyloxy group which may have a substituent.

[0173] —Chemical Structure of L1— In view of the compound's ability to easily absorb light with long wavelengths, L1 in formula (1) is preferably each independently any of the groups represented by formulas (L1-1) to (L1-7) below, more preferably any of the groups represented by formulas (L1-1) to (L1-4) below, and even more preferably a group represented by formula (L1-1) below. In other words, in view of the compound's ability to easily absorb light with long wavelengths, L1 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0174]

[0175] In formulas (L1-1) to (L1-7), R Ｌ１１ are each independently the R Ｄ２ In addition to the definition of R, it is preferable that R further has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom. Ｌ１１ has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, and R Ｌ１１ When a unit adjacent to L1 having the formula (I) has an element capable of non-covalent interaction with at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, R Ｌ１１ And, R Ｌ１１ In other words, in the formed thin film, the planarity of the main skeleton (i.e., the π plane) of the monocyclic or fused ring constituting the aromatic group in L1 is likely to be maintained.

[0176] Specific Examples of L1 Specific examples of L1 include groups represented by the following formulas.

[0177]

[0178] -m- In formula (1), m is an integer of 1 to 4. From the viewpoint of the compound's tendency to absorb light with a long wavelength and the ease of synthesis, m is preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0179] -(L1) ｍ Specific examples of - (L1) ｍ Specific examples of L1 include the specific examples of L1 (i.e., (L1) ｍ In addition to specific examples where m is 1, groups represented by the following formulae are also included.

[0180]

[0181]

[0182] As described above, in formula (1), L1 is preferably a thiophene structure having an alkyloxy group, a thiadiazole structure having an alkyloxy group, a thienothiophene structure having an alkyloxy group, or a thiophene structure having a halogen atom, and more preferably a thiophene structure having an alkyloxy group. ｍ Preferably, the thiophene structure has at least one alkyloxy group-containing thiophene structure, and more preferably, the thiophene structure is an oligomer having an alkyloxy group.

[0183] In the compound of the present disclosure, L1 is preferably a dithienothiophene structure having an alkyloxy group. When m is an integer of 2 to 4, L1 is preferably a thiophene structure having an alkyloxy group, a thiadiazole structure having an alkyloxy group, a thienothiophene structure having an alkyloxy group, or a thiophene structure having a halogen atom, and more preferably a thiophene structure having an alkyloxy group.

[0184] [(L2) ｎ(L2) in formula (1) ｎ In the formula (1), when n is an integer of 2 or more, the chemical structure of each of the L2s present in the formula (1) is independently defined. In other words, the following description of L2s is a description of each of the L2s independently.

[0185] -Aromatic Group- In formula (1), L2 is a divalent aromatic group. The aromatic group in L2 preferably has a monocyclic or fused ring main skeleton. The aromatic group in L2 may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and is preferably an aromatic heterocyclic group from the viewpoint of absorbing long wavelength light. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, and more preferably at least one selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.

[0186] —Chemical Structure of L2— From the viewpoint of the compound's ease of absorbing long-wavelength light, in formula (1), L2 is preferably each independently any of groups represented by formulas (L2-1) to (L2-12) below, more preferably any of groups represented by formulas (L2-1) to (L2-9) below, and even more preferably any of groups represented by formulas (L2-1) to (L2-7) below. That is, from the viewpoint of the compound's ease of absorbing long-wavelength light, L2 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure. Note that, from the viewpoint of the ease of J-association of the compounds of the present disclosure, the chemical structure of L2 is not more limited than the chemical structure of L1.

[0187]

[0188] In formulas (L2-1) to (L2-12), a plurality of R Ｌ２each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amido group, an optionally substituted acid imide group, an optionally substituted substituted carbonyl group, an optionally substituted substituted oxycarbonyl group, an optionally substituted substituted sulfonyl group, an optionally substituted substituted oxysulfonyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkynyl group, a cyano group, or a nitro group.

[0189] Specific Examples of L2 Specific examples of L2 include the above-mentioned specific examples of L1 as well as groups represented by the following formulae.

[0190]

[0191] In formula (1), n ​​is an integer of 0 to 4. When n is 0, that is, (L2) ｎ represents the absence of n, and represents that D and A2 in formula (1) are directly bonded. From the viewpoint of the compound easily absorbing light of a long wavelength and the viewpoint of ease of synthesis, n is preferably an integer of 1 or more, and may be an integer of 2 or more, more preferably an integer of 1 to 4, still more preferably an integer of 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0192] -(L2) ｎSpecific example of - (L2) ｎ Specific examples of L2 include the specific examples of L2 (i.e., (L2) ｎ (Specific examples when n is 1) and the above-mentioned (L1) ｍ In addition to the specific examples above, groups represented by the following formulae are further included.

[0193]

[0194] As described above, in formula (1), L2 is preferably a thiophene structure having an alkyloxy group. ｎ is preferably an oligomer of a thiophene structure having an alkyloxy group.

[0195] In formula (1), when D in formula (1) is the center point, (L1) ｍ The chemical structure of (L2) ｎ The chemical structure of may be point symmetric or asymmetric. In view of the ease with which the compound absorbs light of a long wavelength, it is preferable that m is 2 and n is 1 or 2 in formula (1).

[0196] [A1 and A2: Acceptor] In formula (1), A1 and A2 are each independently a group represented by the following formula (A-1): In each formula, the dotted line represents (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0197]

[0198] In formula (A-1), Ar represents a carbocycle which may have a substituent, or a heterocycle which may have a substituent, and the carbocycle and the heterocycle are each independently a monocycle or a fused ring, and when the carbocycle or the heterocycle has a plurality of substituents, the plurality of substituents may be the same or different.

[0199] The carbocyclic ring may be an aromatic carbocyclic ring. Specific examples of the aromatic carbocyclic ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring. Benzene rings and naphthalene rings are preferred, benzene rings and naphthalene rings are more preferred, and benzene rings are even more preferred. These rings may have a substituent.

[0200] The heterocycle may be an aromatic heterocycle. Specific examples of the aromatic heterocycle include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, and a dibenzophosphole ring, as well as a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.

[0201] —Chemical Structure of A1 and A2— In formula (1), A1 and A2 are preferably each independently any of the groups represented by the following formulae (a-1) to (a-8). In each formula, the symbol “*” indicates (L1) in formula (1). ｍ Bond with or (L2) ｎ The chemical structures of A1 and A2 may be the same or different from each other. From the viewpoint of ease of synthesis of the compound, it is preferable that the chemical structures of A1 and A2 are the same.

[0202]

[0203] In formulas (a-1) to (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group. Ａ１are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, or a cyano group, and more preferably a cyano group. From the viewpoint of the compound being likely to absorb light with a long wavelength, it is preferable that A1 and A2 are each independently a group represented by formula (a-1) or any of formulas (a-4) to (a-8).

[0204] Specific examples of A1 and A2 include groups represented by the following formulae: In each formula, the symbol "*" indicates (L1) in formula (1). ｍ Bond with or (L2) ｎ This shows the bond between .

[0205]

[0206] [Specific Examples of Compounds Represented by Formula (1) of the Present Disclosure] Specific examples of suitable compounds represented by formula (1) of the present disclosure include compounds represented by the following formulas.

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214] -Other n-Type Semiconductor Materials- The n-type semiconductor material may be a compound represented by formula (1) above, or may be two or more n-type semiconductor materials represented by formula (1), or may contain an n-type semiconductor material other than the compound represented by formula (1).

[0215] Examples of low molecular weight compounds that can be included as n-type semiconductor materials other than the compound represented by formula (1) above 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.

[0216] Examples of polymer compounds that can be included as n-type semiconductor materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof.

[0217] The other compound may also be a fullerene derivative.

[0218] Here, the fullerene derivative is a 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."

[0219] The fullerene derivative that can be included as the n-type semiconductor material is not particularly limited as long as it does not impair the object of the present disclosure.

[0220] C that can be included as an n-type semiconductor material ６０ Specific examples of fullerene derivatives include the following compounds.

[0221]

[0222] Above C ６０ In the formula of the fullerene derivative, R represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amido group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group. When there are multiple R's, the multiple R's may be the same or different.

[0223] C ７０ Examples of fullerene derivatives include the following compounds:

[0224]

[0225] (p-Type Semiconductor Material) When the semiconductor material contained in the first layer is a p-type semiconductor material, the preferred p-type semiconductor material, including definitions, examples, preferred aspects, etc., is the same as the definitions, examples, preferred aspects, etc. of the p-type semiconductor material in the [second layer] described below.

[0226] [Second Layer] The active layer of the present disclosure has at least a first layer and a second layer. The second layer contains a semiconductor material of a type different from the semiconductor material contained in the first layer. The second layer may contain an n-type semiconductor material and a p-type semiconductor material, or may contain only a p-type semiconductor material as the semiconductor material. In other words, the second layer may be a single film or a mixed film.

[0227] (n-Type Semiconductor Material) When an n-type semiconductor material is contained in the second layer, the preferred n-type semiconductor material, including definitions, examples, preferred aspects, etc., is the same as the definitions, examples, preferred aspects, etc. of the n-type semiconductor material in the [first layer].

[0228] (P-Type Semiconductor Material) The second layer preferably contains a p-type semiconductor material, and from the viewpoint of improving a high photoelectric conversion rate, the p-type semiconductor material is preferably a hole transport material.

[0229] The p-type semiconductor material is preferably a polymer compound having a predetermined weight average molecular weight in terms of polystyrene.

[0230] Here, the weight average molecular weight in terms of polystyrene refers to a weight average molecular weight calculated using a polystyrene standard sample by gel permeation chromatography (GPC).

[0231] The weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in a solvent.

[0232] The p-type semiconductor material is preferably a π-conjugated polymer compound (also referred to as a DA-type conjugated polymer compound) containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit). Whether one is a donor structural unit or an acceptor structural unit can be determined relatively from the energy levels of the HOMO or LUMO.

[0233] 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.

[0234] In the present disclosure, structural units that can constitute a p-type semiconductor material include structural units in which a donor structural unit and an acceptor structural unit are directly bonded, as well as structural units in which a donor structural unit and an acceptor structural unit are bonded via any suitable spacer (group or structural unit).

[0235] 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.

[0236] The second layer preferably contains a p-type semiconductor material, and the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The structural unit represented by the following formula (3) is usually preferably a donor structural unit. The structural unit represented by the following formula (4) is usually preferably an acceptor structural unit.

[0237]

[0238] -Formula (3)- In formula (3), Ar ３ and Ar ４each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulas (Z-1) to (Z-7):

[0239]

[0240] In formulas (Z-1) to (Z-7), R is independently defined as C ６０ The definition of R is the same as that of the fullerene derivative. In each of formulas (Z-1) to (Z-7), when there are two R, the two R may be the same or different.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] 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.

[0245] The constitutional unit represented by formula (3) is preferably a constitutional unit represented by the following formula (3-1), (3-2) or (3-3).

[0246]

[0247] In formulas (3-1), (3-2) and (3-3), Ar ３ , Ar ４ and R are defined as Ar in formula (3). ３ , Ar ４ Definition of C ６０ The definition of R in the formula of the fullerene derivative is as follows.

[0248] Specific examples of suitable structural units represented by formula (3) include structural units represented by the following formulas:

[0249]

[0250] In the above formula, the definition of R is the same as the definition of R in formulas (Z-1) to (Z-7). When there are two R, the two R may be the same or different.

[0251] More specific examples of preferred structural units represented by formula (3) include structural units represented by the following formulas:

[0252]

[0253] -Formula (4)- In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

[0254] Ar ５The divalent aromatic heterocyclic group represented by the formula (I) preferably has 2 to 60 carbon atoms, more preferably 4 to 60 carbon atoms, and even more preferably 4 to 20 carbon atoms.

[0255] Ar ５ The divalent aromatic heterocyclic group represented by the following formula (1) may have a substituent. ５ Examples of the substituent that the divalent aromatic heterocyclic group represented by the formula (I) may have include a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted monovalent heterocyclic group, an optionally substituted substituted amino group, an optionally substituted acyl group, an optionally substituted imine residue, an optionally substituted amide group, an optionally substituted acid imide group, an optionally substituted substituted oxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a cyano group, and a nitro group.

[0256] As the constitutional unit represented by formula (4), constitutional units represented by the following formulae (4-1) to (4-10) are preferred.

[0257]

[0258] In formulas (4-1) to (4-10), R is C ６０ The definition of R in the formula of the fullerene derivative is as follows. ３ and X ４ each independently represents an oxygen atom or a sulfur atom. １ and Z ２ each independently represents a group represented by ═C(R)— or a nitrogen atom. When there are two R, the two R may be the same or different.

[0259] X in formula (4-1) to formula (4-10) ３ and X ４ are preferably sulfur atoms from the viewpoint of availability of raw material compounds.

[0260] As described above, the structural units represented by formulas (4-1) to (4-10) can generally function as acceptor structural units. However, without being limited thereto, the structural units represented by formulas (4-4), (4-5), and (4-7) in particular can also function as donor structural units.

[0261] 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.

[0262] Ar ５ Specific examples of the divalent aromatic heterocyclic group represented by the formula (101) include groups represented by the following formulas (101) to (191). These groups may further have a substituent.

[0263]

[0264]

[0265]

[0266]

[0267] The polymer compound that is a p-type semiconductor material is preferably a π-conjugated polymer compound that includes a constitutional unit represented by formula (3) as a donor constitutional unit and a constitutional unit represented by formula (4) as an acceptor constitutional unit.

[0268] In the polymer compound that is a p-type semiconductor material, the polymer compound that is a p-type semiconductor material may include, as a structural unit, a structure in which the structural unit represented by formula (3) and the structural unit represented by formula (4) already described are linked together.

[0269] The polymer compound that is a p-type semiconductor material may contain two or more types of constitutional units represented by formula (3), or may contain two or more types of constitutional units represented by formula (4).

[0270] For example, from the viewpoint of improving solubility in a solvent, the polymer compound that is a p-type semiconductor material may contain a constitutional unit represented by the following formula (5).

[0271]

[0272] In formula (5), Ar ６ represents an arylene group.

[0273] Ar ６ The arylene group represented by the formula (I) means an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon also includes a compound having a fused ring and a compound in which two or more rings selected from the group consisting of independent benzene rings and fused rings are bonded together directly or via a divalent group such as a vinylene group.

[0274] 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.

[0275] Ar ６ The number of carbon atoms of the arylene group represented by the formula (I) is usually preferably 6 to 60, not including the number of carbon atoms of the substituent, and more preferably 6 to 20. The number of carbon atoms of the arylene group including the substituent is usually preferably 6 to 100.

[0276] Ar ６ Examples of the arylene group represented by the formula (I) include a phenylene group (e.g., Formulas 1 to 3 below), a naphthalene-diyl group (e.g., Formulas 4 to 13 below), an anthracene-diyl group (e.g., Formulas 14 to 19 below), a biphenyl-diyl group (e.g., Formulas 20 to 25 below), a terphenyl-diyl group (e.g., Formulas 26 to 28 below), a fused ring compound group (e.g., Formulas 29 to 35 below), a fluorene-diyl group (e.g., Formulas 36 to 38 below), and a benzofluorene-diyl group (e.g., Formulas 39 to 46 below).

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285] In the formula, R is defined as C ６０ The definition of R is the same as that of the fullerene derivative. Multiple Rs may be the same or different.

[0286] The constitutional unit represented by formula (5) is preferably a constitutional unit represented by the following formula (5-1) or formula (5-2).

[0287]

[0288] In the formula (5-1) and the formula (5-2), R is defined as C ６０ The definition of R is the same as that of R in the formula of the fullerene derivative. The two R may be the same or different.

[0289] 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.

[0290] When the polymer compound as a p-type semiconductor material contains a constitutional unit represented by formula (3) and / or a constitutional unit represented by formula (4), the total amount of the constitutional unit represented by formula (3) and the constitutional unit represented by formula (4) is usually preferably 20 mol% to 100 mol%, and from the viewpoint of improving the charge transport property as a p-type semiconductor material, is more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%, when the amount of all constitutional units contained in the polymer compound is taken as 100 mol%.

[0291] Specific examples of polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas (P-1) to (P-19).

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300] In the above formula, R is defined as C ６０ The definition of R is the same as that of the fullerene derivative. Multiple Rs may be the same or different.

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

[0302] [Other Layers] In addition to the first and second layers, the active layer of the present disclosure may include other layers, such as a third layer, a fourth layer, or a fifth layer. The active layer may have any number of layers, from 2 to 6 layers, or may have 2 to 3 layers, with 2 layers being preferred. The other layers may each independently be a single film containing either a p-type semiconductor material or an n-type semiconductor material, or may be a mixed film containing a p-type semiconductor material and an n-type semiconductor material. The other layers may be provided so as to be in contact with the first layer or the second layer, or may be provided between the first and second layers.

[0303] <Substrate> The photoelectric conversion element is usually preferably 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 does not chemically change, particularly when a layer containing an organic compound is formed.

[0304] 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.

[0305] <Electrodes> The photoelectric conversion element preferably includes a pair of electrodes, an anode and a cathode. At least one of the anode and the cathode is preferably a transparent or semi-transparent electrode to allow light to enter.

[0306] Examples of transparent or translucent electrode materials include conductive metal oxide films and translucent metal thin films. Specific examples include conductive materials such as indium oxide, zinc oxide, tin oxide, and their composites, such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, as well as gold, platinum, silver, and copper. Preferred transparent or translucent electrode materials are ITO, IZO, and tin oxide. Alternatively, transparent conductive films made of organic compounds such as polyaniline and its derivatives, polythiophene and its derivatives, etc. may be used as electrodes. The transparent or translucent electrode may be an anode or a cathode.

[0307] As long as one electrode of a pair of electrodes is transparent or translucent, the other electrode may have low optical transparency. Examples of materials for the electrode with low optical transparency include metals and conductive polymers. Specific examples of materials for the electrode with low optical transparency include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, and ytterbium, alloys of two or more of these metals, alloys of one or more of these metals with one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, graphite, graphite intercalation compounds, polyaniline and its derivatives, and polythiophene and its derivatives. The alloys include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

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

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

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

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

[0312] The hole transport layer contains a hole transport material. Examples of the hole transport material include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing a structural unit having an aromatic amine residue, CuSCN, CuI, NiO, and tungsten oxide (WO ３ ) and molybdenum oxide (MoO ３ Examples of hole transporting material products include Avantama P-10 and P-21.

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

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

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

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

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

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

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

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

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

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

[0323] 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.

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

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

[0326] <Applications of Photoelectric Conversion Element> Applications of the photoelectric conversion element of the present disclosure include photodetection elements and solar cells. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from the transparent or semitransparent electrode side while applying a voltage (reverse bias voltage) between the electrodes, and can operate as a photodetection element (photosensor). Furthermore, by integrating a plurality of photodetection elements, the element can also be used as an image sensor. In this way, the photoelectric conversion element of the present disclosure can be particularly suitably used as a photodetection element.

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

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

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

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

[0331] <Method for manufacturing photoelectric conversion element> The method for manufacturing the photoelectric conversion element of the present disclosure is not particularly limited. The photoelectric conversion element of the present disclosure can be manufactured by combining a suitable forming method with materials selected for forming the components.

[0332] The method for manufacturing a photoelectric conversion element according to the present disclosure may include a step including a heating treatment at a heating temperature of 100° C. or higher. More specifically, the active layer may be formed by a step including a heating treatment at a heating temperature of 100° 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.

[0333] Hereinafter, a method for manufacturing a photoelectric conversion element having a structure in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are in contact with one another in this order will be described.

[0334] (Substrate Preparation Step) In this step, for example, a support substrate provided with an anode is prepared. Alternatively, a substrate provided with a conductive thin film formed from the electrode material already described may be purchased from the market, and the conductive thin film may be patterned to form an anode, as necessary, to prepare a support substrate provided with an anode.

[0335] In the method for producing a photoelectric conversion element according to the present disclosure, the method for forming an anode on a supporting substrate is not particularly limited. The anode can be formed on a structure where the anode is to be formed (e.g., a supporting substrate, an active layer, a hole transport layer) by any suitable conventional method such as vacuum deposition, sputtering, ion plating, plating, or coating using the materials already described.

[0336] (Step of Forming Hole Transport Layer) The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the anode.

[0337] 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.

[0338] (Active Layer Forming Process) In the method for producing a photoelectric conversion element of the present disclosure, an active layer is formed on a hole transport layer. The active layer, which is a main component, can be formed by any suitable conventionally known forming process. The active layer is preferably produced by a coating method using an ink (coating liquid) containing a semiconductor material. Preferred embodiments of the ink containing a semiconductor material are as described above.

[0339] Hereinafter, steps (i) and (ii) included in the process of forming the active layer, which is a main component of the present disclosure, will be described.

[0340] Step (i) Any suitable coating method can be used as a method for applying the ink to a coating target. As the coating method, slit coating, knife coating, spin coating, microgravure coating, gravure coating, bar coating, inkjet printing, nozzle coating, or capillary coating is preferred, slit coating, spin coating, capillary coating, or bar coating is more preferred, and slit coating or spin coating is even more preferred.

[0341] 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.

[0342] Step (ii) Any suitable method can be used to remove the solvent from the ink coating, i.e., to remove the solvent from the coating and solidify it. Examples of the method for removing the solvent include a method of directly heating using a hot plate under an inert gas atmosphere such as nitrogen gas, hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

[0343] In the method for producing a photoelectric conversion element according to the present disclosure, step (ii) is a step for volatilizing and removing the solvent, and is also referred to as a pre-baking step (first heat treatment step).

[0344] 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, etc.

[0345] In the method for producing a photoelectric conversion element according to the present disclosure, specifically, for example, the pre-baking step and the post-baking step can be carried out using a hot plate in an air atmosphere or a nitrogen gas atmosphere.

[0346] The heating temperature in the pre-baking step is usually preferably about 70 to 100° C. Specifically, the heating temperature in the pre-baking step and / or the post-baking step can be 40° C. or higher, preferably about 70 to 100° C., and further can be 120° C. or higher. The upper limit of the heating temperature is preferably 280° C. or lower, more preferably 250° C. or lower.

[0347] The total heat treatment time in the pre-bake step and post-bake step may be, for example, one hour.

[0348] The heating temperature in the pre-baking step and the heating temperature in the post-baking step may be the same or different.

[0349] The heat treatment time can be, for example, 10 minutes or more. The upper limit of the heat treatment time is not particularly limited, but can be, for example, 4 hours in consideration of the takt time and the like.

[0350] The thickness of the active layer can be adjusted to any desired thickness by appropriately adjusting the solid content concentration in the coating solution and the conditions of step (i) and / or step (ii).

[0351] The thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness taking into consideration the balance between suppressing dark current and extracting the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more, particularly from the viewpoint of further reducing dark current. 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. The preferred active layer thickness may be the thickness of one active layer or the total thickness of multiple active layers.

[0352] The step of forming the active layer may include other steps in addition to the steps (i) and (ii), provided that the other steps do not impair the object and effect of the present disclosure.

[0353] The method for producing a photoelectric conversion element according to the present disclosure may be a method for producing a photoelectric conversion element including a plurality of active layers, or may be a method in which step (i) and step (ii) are repeated a plurality of times.

[0354] In the photoelectric conversion element of the present disclosure, the active layer has at least a first layer and a second layer. Therefore, the method for manufacturing a photoelectric conversion element of the present disclosure includes at least forming a first layer and forming a second layer. The method for forming each layer is not particularly limited and may include, for example, applying an ink containing a mixture of a semiconductor material and a solvent. From the viewpoint of easily obtaining a PHJ structure, it is preferable that the ink used to form the first layer and the ink used to form the second layer each use different solvents. The solvent is preferably either xylene, 1,2-dimethylbenzene, a mixed solvent of chloroform and chloronaphthalene (e.g., a 98:2 volume ratio), or toluene. From the viewpoint of ease of dissolution, it is preferable to use xylene as the solvent for p-type semiconductor materials and toluene as the solvent for n-type semiconductor materials.

[0355] The method for manufacturing a photoelectric conversion element according to the present disclosure preferably includes a step of forming an electron transport layer (electron injection layer) on the active layer.

[0356] 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 coating method or vacuum deposition method.

[0357] (Cathode Formation Process) The method for forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by, for example, applying the above-exemplified electrode material to the electron transport layer by any suitable conventional method such as a coating method, a vacuum deposition method, a sputtering method, an ion plating method, or a plating method. The photoelectric conversion element of the present disclosure is preferably manufactured by the above-described process.

[0358] (Sealed body forming process) When forming the sealed body, any suitable sealing material (adhesive) and substrate (sealing substrate) known in the art are used. Specifically, a sealing material such as a UV-curable resin is applied to a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the support substrate and the sealing material are bonded together without any gaps. After that, the photoelectric conversion element is sealed in the gap between the support substrate and the sealing substrate using a method suitable for the selected sealing material, such as irradiation with UV light, thereby obtaining a sealed photoelectric conversion element.

[0359] <Photodetector> As described above, the photoelectric conversion element of the present disclosure, particularly the photodetector (optical sensor), can function by being incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device).

[0360] 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 100° C. or higher.

[0361] The heat treatment time can be, for example, 10 minutes or more. The upper limit of the heat treatment time is not particularly limited, but can be, for example, 4 hours in consideration of the takt time and the like.

[0362] Examples are provided below to further explain the present disclosure, but the present disclosure is not limited to the examples described below.

[0363] <Preparation of Active Layer> An active layer was prepared using a p-type semiconductor material and an n-type semiconductor material.

[0364] [P-Type Semiconductor Material] The polymer compounds shown in Table 1 below were used as p-type semiconductor materials (electron-donating compounds).

[0365]

[0366] Polymer compound P-1, a p-type semiconductor material, was obtained commercially under the trade name PCE10 / PTB7-Th (trade name, manufactured by 1-material). Polymer compound P-2, a p-type semiconductor material, was synthesized and used with reference to the method described in WO 2013 / 051676. Polymer compound P-3, a p-type semiconductor material, was synthesized and used with reference to the method described in WO 2011 / 052709. Polymer compound P-4, a p-type semiconductor material, was obtained commercially under the trade name PM6 (trade name, manufactured by 1-material).

[0367] [n-Type Semiconductor Materials] The compounds shown in Tables 2 to 4 below were used as n-type semiconductor materials (electron-accepting compounds).

[0368]

[0369]

[0370]

[0371] (Synthesis of Compound N-1) Compound 2 was synthesized using Compound 1.

[0372]

[0373] In a 300 mL four-neck flask, 3-methoxythiophene (Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH.H ２ O (0.833 g, 4.38 mmol) and toluene (100 g) were charged, purged with nitrogen, and then heated to 110°C. After stirring for 23 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane = 100 wt%) to obtain 13.4 g of compound 2 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 2 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.21 (1H), 3.81 (2H), 1.77-1.71 (1H), 1.46-1.28 (m, 24H), 0.90-0.86 (m, 6H)

[0374] Compound 3 was synthesized using compound 2.

[0375]

[0376] A 1 L four-neck flask was charged with compound 2 (15.4 g, 47.3 mmol) and THF (461 g), and the flask was purged with nitrogen and then cooled to 0°C. NBS (8.33 g, 46.8 mmol) was added and the mixture was stirred at 0°C. After stirring for 2 hours, quenching was performed by pouring in a 3 wt% aqueous solution of sodium sulfite (249 g). After warming to room temperature, the aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane = 100 wt%) to obtain 18.5 g of compound 3 as a colorless, transparent liquid.

[0377] Compound 4 was synthesized using compound 3.

[0378]

[0379] A 50 mL four-neck flask was charged with compound 3 (18.5 g, 45.9 mmol) and THF (185 g). The flask was purged with nitrogen and then cooled to -73°C. LDA (1 M in THF / Hexane, 45.9 mL, 45.9 mmol) was added and the mixture was kept at -73°C for 2 hours. DMF (7.1 mL, 91.9 mmol) was slowly added, and the mixture was warmed to room temperature and stirred for 2 hours. After quenching by pouring 20% ​​aqueous ammonium chloride solution (98 mL), the aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 70 / 1 (volume ratio)) to obtain 5.26 g of compound 4 as a yellow liquid. The NMR spectrum of the resulting compound 4 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.70 (1H), 7.37 (1H), 3.95 (2H), 1.80-1.74 (1H), 1.49-1.27 (m, 24H), 0.90-0.86 (m, 6H)

[0380] Compound 6 was synthesized using compound 5.

[0381]

[0382] In a 50 mL four-neck flask, 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 0.477 g, 1.18 mmol), bis(pinacolato)diboron (0.752 g, 3.0 mmol), and [Ir(OMe)(cod)] were added. ２(9 mg, 0.01 mmol) and tBu-bpy (8 mg, 0.02 mmol) were charged and purged with nitrogen, after which 7 g of cyclohexane was charged and the mixture was kept warm in an oil bath heated to 60°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The cooled mass was poured into water for quenching. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered while passing the liquid through silica gel, and then the entire amount was concentrated using a rotary evaporator to obtain 0.802 g of the crude target product.

[0383] Compound 7 was synthesized using Compound 6 and Compound 4.

[0384]

[0385] A 100 mL four-neck flask was charged with crude compound 6 (3.36 g), compound 4 (5.09 g, 11.8 mmol), and THF (30.2 g), and nitrogen was bubbled through for 30 minutes. ２ (dba) ３ (0.235g, 0.257mmol), P(tBu ３ ) HBF ４ (0.149g, 0.513mmol), 3mol / L of K ３ P.O. ４ The mixture was then charged with an aqueous solution (9.50 g) and heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane / ethyl acetate = 30 / 1 (volume ratio)) to obtain 3.28 g of compound 7 as a red viscous liquid.

[0386] Compound 7 was used to synthesize compound N-1.

[0387]

[0388] In a 200 mL four-neck flask, compound 7 (3.28 g, 2.97 mmol), compound 7-1 (2.18 g, 8.91 mmol) synthesized according to the method described in WO 2020 / 109823, p-TsOH.H ２O (1.70 g, 8.91 mmol), EtOH (29.5 g), toluene (65.6 g), MgSO ４ (1.64 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 3.41 g (yield 74%) of compound N-1 as a blue-green black solid. The NMR spectrum of the obtained compound N-1 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.01 (2H), 8.80 (2H), 8.17 (2H), 7.74 (2H), 7.54 (2H), 4.19 (4H), 2.01-1.95 (m, 6H), 1.58-0.63 (m, 90H)

[0389] (Synthesis of Compound N-2) Compound 9 was synthesized using compound 8.

[0390]

[0391] In a 300 mL four-neck flask, 3-methoxythiophene (Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH.H ２ O (0.833 g, 4.38 mmol) and toluene (100 g) were charged, purged with nitrogen, and then heated to 110°C. After stirring for 23 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: hexane = 100 wt%) to obtain 13.4 g of compound 9 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 9 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.21 (1H), 3.81 (2H), 1.77-1.71 (1H), 1.46-1.28 (m, 24H), 0.90-0.86 (m, 6H)

[0392] Compound 10 was synthesized using compound 9.

[0393]

[0394] A 200 mL four-neck flask was charged with compound 9 (4.0 g, 12.3 mmol) and THF (45 mL), and the flask was purged with nitrogen and then cooled to -73°C. LDA (1 M in THF / Hexane, 13.6 mL, 13.6 mmol) was charged, and the flask was maintained at an internal temperature of -65°C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.2 mL, 18.5 mmol) and THF (22.5 mL) were charged into a dropping funnel, and the flask was gradually added dropwise to the reaction mass at an internal temperature of -65°C. After the dropwise addition was completed, the flask was maintained at an internal temperature of -65°C for 1 hour, then heated to room temperature, and stirred for 2 hours. After quenching by pouring in 20% aqueous ammonium chloride solution (26 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 5.91 g of compound 10 as a crude product. The NMR spectrum of the resulting compound 10 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.26 (1H), 6.56 (1H), 3.82 (2H), 1.74-1.72 (1H), 1.57-1.19 (m, 36H), 00.88 (6H)

[0395] Compound 11 was synthesized using compound 10.

[0396]

[0397] A 500 mL four-neck flask was charged with crude compound 10 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and THF (149 mL), and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.600g, 0.655mmol), P(tBu ３ ) HBF ４ (0.399g, 1.38mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with toluene and then an aqueous solution (60.6 g), and then heated to 65°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 3.72 g of compound 11 as a yellow-brown liquid. The NMR spectrum of the obtained compound 11 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.08 (1H), 6.29 (1H), 4.06 (2H), 3.83 (2H), 1.85-1.27 (m, 34H), 0.98-0.86 (m, 12H)

[0398] Compound 12 was synthesized using compound 11.

[0399]

[0400] A 100 mL four-neck flask was charged with compound 11 (1.60 g, 2.84 mmol) and chloroform (56.0 g). The flask was purged with nitrogen and then cooled to 0°C. NBS (0.501 g, 2.81 mmol) was added and stirred at 0°C. After stirring for 2 hours, water (40.0 g) was added and the mixture was warmed to room temperature. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 1.84 g of compound 12 as a yellow-brown liquid. The NMR spectrum of the resulting compound 12 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (1H), 7.45 (1H), 7.02 (1H), 4.07 (2H), 3.93 (2H), 1.86-1.27 (m, 34H), 0.99-0.86 (m, 12H)

[0401] Compound 14 was synthesized using compound 13.

[0402]

[0403] A 50 mL four-neck flask was charged with 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol) and THF (11.2 mL), and after purging with nitrogen, the flask was cooled to -73°C. nBuLi (1.56 mol / L in hexane, 1.75 mL, 2.73 mmol) was then charged, and the flask was kept at an internal temperature of -65°C for 1 hour. A dropping funnel was charged with 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.85 mL, 3.72 mmol) and THF (5.6 mL), and the mixture was added dropwise little by little to the reaction mass at an internal temperature of -65°C. After the addition was completed, the mixture was kept at an internal temperature of -65°C for 1 hour, then heated to room temperature, and stirred for 1 hour. After quenching by pouring 20% ​​aqueous ammonium chloride solution (5.3 mL), the aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then totally concentrated using a rotary evaporator to obtain 1.49 g of crude compound 14.

[0404] Compound 15 was synthesized using compound 14 and compound 12.

[0405]

[0406] Crude compound 14 (1.49 g), compound 12 (2.05 g, 3.20 mmol), and THF (29.6 g) were placed in a 100 mL four-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.113g, 0.123mmol), P(tBu ３ ) HBF ４ (0.0749g, 0.258mmol), 3mol / L of K ３ P.O. ４The mixture was charged with toluene and then an aqueous solution (11.4 g) of toluene, and then heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 1.27 g of compound 15 as a red liquid. The NMR spectrum of the resulting compound 15 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.20 (1H), 7.13-7.10 (m, 2H), 6.93-6.91 (m, 1H), 4.10 (2H), 4.05 (2H), 1.93-0.57 (m, 80H)

[0407] Compound 16 was synthesized using compound 15.

[0408]

[0409] In a 50 mL four-neck flask, compound 15 (1.25 g, 1.30 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.497 g, 1.56 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and Pd(OAc) were placed. ２ (0.0364g, 0.162mmol), [(tBu) ２ MePH]BF ４ (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), K ２ CO ３(0.538 g, 3.89 mmol) and DMF (12.5 g) were charged and nitrogen bubbling was performed for 30 minutes. After nitrogen replacement, the internal temperature was raised to 120°C and stirred for 5 hours. After cooling to room temperature, it was diluted with toluene and washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.620 g of compound 16 as a deep red-purple liquid. The NMR spectrum of the obtained compound 16 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.74 (1H), 7.47 (2H), 7.32 (1H), 7.20 (1H), 7.12 (1H), 4.13 -4.06 (m, 6H), 1.89-0.60 (m, 95H)

[0410] Compound 16 was used to synthesize compound N-2.

[0411]

[0412] A 50 mL four-neck flask was charged with compound 16 (0.600 g, 0.499 mmol), compound 7-1 (0.366 g, 1.50 mmol) synthesized according to the method described in WO 2020 / 109823, and p-TsOH.H ２ O (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), MgSO ４ (0.300 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating using an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified using a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.632 g (yield 78%) of compound N-2 as a black solid. The NMR spectrum of the obtained compound N-2 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 8.98-8.95 (m, 2H), 8.76-8.72 (m, 2H), 8.14-8.11 (m, 2H), 7.74 (1H), 7.50-7.32 (m, 4H), 4.19 (6H), 2.06-0.64 (m, 95H)

[0413] (Synthesis of Compound N-3) Compound 19 was synthesized using compound 18.

[0414]

[0415] In a 50 mL four-neck flask, 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol), bis(pinacolato)diboron (1.58 g, 6.21 mmol), and [Ir(OMe)(cod)] were added. ２ (19.8 mg, 0.0298 mmol), tBu-bpy (16.0 mg, 0.0596 mmol) were charged and the mixture was purged with nitrogen, after which 15.0 g of cyclohexane was charged and the mixture was kept warm in an oil bath heated to 60°C. After stirring for 2 hours, the mixture was removed from the oil bath and allowed to cool to room temperature. The cooled mass was poured into water for quenching. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered while passing the mixture through silica gel, and then totally concentrated using a rotary evaporator to obtain 2.30 g of crude compound 19.

[0416] Compound 20 was synthesized using compound 19 and compound 12.

[0417]

[0418] Crude compound 19 (1.13 g), compound 12 (1.80 g, 2.81 mmol), and THF (18.2 g) were placed in a 50 mL four-neck flask, and nitrogen bubbling was carried out for 30 minutes. ２ (dba) ３ (0.0560g, 0.0612mmol), P(tBu ３ ) HBF ４ (0.0372 g, 0.128 mmol), 3 mol / L K３ P.O. ４ The mixture was charged with toluene and then an aqueous solution (5.66 g), and then heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 1.19 g of compound 20 as a deep red viscous liquid. The NMR spectrum of the resulting compound 20 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.46 (2H), 7.20 (2H), 7.13 (2H), 4.10 (4H), 4.06 (2H), 1.94-0.61 (m, 126H)

[0419] Compound 20 was used to synthesize compound N-3.

[0420]

[0421] In a 100 mL four-neck flask, compound 20 (1.15 g, 0.754 mmol), compound 7-1 (0.553 g, 2.26 mmol), and p-TsOH.H ２ O (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), MgSO ４ (0.575 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.890 g (yield 60%) of compound N-3 as a black solid. The NMR spectrum of the obtained compound N-3 was analyzed. The results are as follows. １H-NMR (300 MHz, CHLOROFORM-D) δ 8.94-8.93 (m, 2H), 8.69 (2H), 8.10 (2H), 7.50-7.35 (m, 6H), 4.19-4.15 (m, 8H), 1.94-0.64 (m, 126H)

[0422] (Synthesis of Compound N-4) Compound 21 was synthesized using Compound 8.

[0423]

[0424] In a 300 mL four-neck flask, 3-methoxythiophene (Tokyo Chemical Industry Co., Ltd., 4.50 g, 39.4 mmol), 2-ethyl-1-hexanol (15.4 g, 118 mmol), p-TsOH.H ２ O (0.750 g, 3.94 mmol) and toluene (90 g) were charged, purged with nitrogen, and then heated to 110°C. After stirring for 7 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane = 100 wt%) to obtain 8.08 g of compound 21 as a colorless, transparent liquid. The NMR spectrum of the resulting compound 21 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.22 (1H), 3.83 (2H), 1.74-1.64 (1H), 1.54-1.27 (m, 8H), 0.95-0.86 (m, 6H)

[0425] Compound 22 was synthesized using compound 21.

[0426]

[0427] A 100 mL four-neck flask was charged with compound 21 (2.0 g, 9.42 mmol) and THF (22.5 mL), and the flask was purged with nitrogen and then cooled to -73°C. LDA (1 M in THF / Hexane, 11.3 mL, 11.3 mmol) was charged, and the flask was maintained at an internal temperature of -65°C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.2 mL, 14.1 mmol) and THF (11.2 mL) were charged into a dropping funnel, and the flask was gradually added dropwise to a reaction mass whose internal temperature was -65°C. After completion of the dropwise addition, the flask was maintained at an internal temperature of -65°C for 1 hour, then heated to room temperature, and stirred for 2 hours. After quenching by pouring in 20% aqueous ammonium chloride solution (20 mL), the aqueous layer was separated from the resulting mass, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator to obtain 3.13 g of compound 22 as a crude product. The NMR spectrum of the resulting compound 22 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 7.26 (1H), 6.57 (1H), 3.83 (2H), 1.73-1.63 (1H), 1.54-1.20 (m, 20H), 00.95-0.86 (m, 6H)

[0428] Compound 22 was used to synthesize compound 23.

[0429]

[0430] A 100 mL four-neck flask was charged with crude compound 22 (3.10 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (3.22 g, 10.1 mmol) (manufactured by JiangSu GR-Chem Co., Ltd.), and THF (31.4 mL), and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.420g, 0.458mmol), P(tBu ３ ) HBF ４ (0.279g, 0.962mmol), 3mol / L of K ３ P.O. ４The mixture was charged with toluene and then an aqueous solution (17.0 g) of toluene, and then heated to 65°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 15 / 1 (volume ratio)) to obtain 2.81 g of compound 23 as a yellow-brown liquid. The NMR spectrum of the resulting compound 23 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 7.46 (1H), 7.09 (1H), 6.29 (1H), 4.06 (2H), 3.85 (2H), 1.85-1.27 (m, 18H), 0.98-0.86 (m, 12H)

[0431] Compound 24 was synthesized using compound 23.

[0432]

[0433] A 100 mL four-neck flask was charged with compound 23 (1.15 g, 2.55 mmol) and chloroform (40.3 g). The flask was purged with nitrogen and then cooled to 0°C. NBS (0.450 g, 2.53 mmol) was added and stirred at 0°C. After stirring for 2 hours, water (28.8 g) was added and the mixture was warmed to room temperature. The aqueous layer was removed from the resulting mass by separation, dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 15 / 1 (volume ratio)) to obtain 1.28 g of compound 24 as a yellow liquid. The NMR spectrum of the resulting compound 24 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (1H), 7.45 (1H), 7.03 (1H), 4.07 (2H), 3.95 (2H), 1.84-1.27 (m, 18H), 0.99-0.86 (m, 12H)

[0434] Compound 26 was synthesized using compound 25.

[0435]

[0436] A 50 mL four-neck flask was charged with 4,8-Bis(3,5-dioctyl-2-thienyl)-2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[1,2-b:4,5-b']dithiophene (0.956 g, 0.906 mmol), Compound 24 (1.20 g, 2.27 mmol), and THF (21.8 g), and nitrogen bubbling was performed for 30 minutes. ２ (dba) ３ (0.0415g, 0.045mmol), P(tBu ３ ) HBF ４ (0.0276g, 0.095mmol), 3mol / L of K ３ P.O. ４ The mixture was charged with toluene and then an aqueous solution (4.19 g) of toluene, and then heated to 60°C. After stirring for 2 hours, the mixture was cooled to room temperature. The mixture was diluted with toluene and washed twice with water, then dried over magnesium sulfate, filtered, and then completely concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (developing solvent: heptane / ethyl acetate = 7 / 1 (volume ratio)) to obtain 0.90 g of compound 26 as a red viscous liquid. The NMR spectrum of the resulting compound 26 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ9.75 (2H), 7.46 (2H), 7.40-7.39 (2H), 7.18 (2H), 6.78 (2H), 4.13-3.98 (m, 8H), 2.27 (4H), 2.45-2.37 (m, 4H), 1.85-0.70 (m, 120H)

[0437] Compound 26 was used to synthesize compound N-4.

[0438]

[0439] In a 50 mL four-neck flask, compound 26 (0.500 g, 0.294 mmol), compound 7-1 (0.215 g, 0.882 mmol), and p-TsOH.H ２O (0.168 g, 0.882 mmol), EtOH (4.6 g), toluene (10.0 g), MgSO ４ (0.250 g) was charged and kept warm in an oil bath heated to 65°C. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. ４ After removing the solvent, the precipitate was dissolved and washed with chloroform. After concentrating with an evaporator, a crude product was obtained by repulping and washing with methanol. The obtained crude product was purified with a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.46 g (yield 73%) of compound N-4 as a black solid. The NMR spectrum of the obtained compound N-4 was analyzed. The results are as follows. １ H-NMR (300 MHz, CHLOROFORM-D) δ8.93-8.70 (4H), 8.13 (2H), 7.53-7.23 (6H), 6.81 (2H), 4.14 (8H), 3.01-2.88 (m, 4H), 2.44-2.21 (m, 4H), 1.91-0.61 (m, 120H)

[0440] (Synthesis of Compound N-10) Compound N-10 was synthesized according to the following scheme.

[0441]

[0442]

[0443] For compound N-5, which is an n-type semiconductor material, SiOTIC-4F (trade name, manufactured by 1-material) was purchased commercially and used. For compound N-6, which is an n-type semiconductor material, IEICO-4F (trade name, manufactured by 1-material) was purchased commercially and used. For compound N-7, which is an n-type semiconductor material, COTIC-4F (trade name, manufactured by 1-material) was purchased commercially and used. For compound N-8, which is an n-type semiconductor material, COTIC-4Cl (trade name, manufactured by 1-material) was purchased commercially and used. For compound N-9, which is an n-type semiconductor material, COI-4Cl (trade name, manufactured by 1-material) was purchased commercially and used.

[0444] [Preparation of Ink] (Preparation of Ink (I-1)) As shown in Table 5 below, Compound P-1, a p-type semiconductor material (polymer compound), was stirred in 1,2-dimethylbenzene as a solvent at 60°C for 8 hours to give a concentration of 1 mass % relative to the total mass of the ink, and the resulting mixture was filtered using a filter to obtain Ink (I-1).

[0445] (Preparation of Inks (I-2) to (I-4)) Inks (I-2) to (I-4) were prepared in the same manner as for ink (I-1), using the p-type semiconductor materials shown in Table 5.

[0446]

[0447] (Preparation of Ink (I-5)) As shown in Table 6 below, Compound N-1, an n-type semiconductor material (polymer compound), was stirred at 60°C for 8 hours in a toluene solvent so that the concentration would be 1% by mass relative to the total mass of the ink. The resulting mixture was then filtered using a filter to obtain Ink (I-5).

[0448] (Preparation of Inks (I-6) to (I-13) and (I-36)) Inks (I-6) to (I-13) and (I-36) were prepared in the same manner as for ink (I-5), except that the n-type semiconductor materials shown in Table 6 were used.

[0449]

[0450] (Preparation of Ink (I-14)) As shown in Table 7 below, Compound N-1, an n-type semiconductor material, and Polymer Compound P-1, a p-type semiconductor material, were mixed into a solvent mixture of chloroform and chloronaphthalene (volume ratio of 98:2) to give an n-type semiconductor material at a concentration of 1 mass % relative to the total mass of the ink, and Polymer Compound P-1, a p-type semiconductor material, at a concentration of 1 mass % relative to the total mass of the ink (n-type semiconductor material / p-type semiconductor material=1 / 1). The mixture was stirred at room temperature for 8 hours, and the resulting mixture was filtered using a filter to give Ink (I-14).

[0451] (Preparation of Inks (I-15) to (I-35) and (I-37)) Inks (I-15) to (I-35) and (I-37) were prepared in the same manner as for ink (I-14), except that the n-type semiconductor material and p-type semiconductor material were used in the combinations shown in Table 7 below.

[0452]

[0453] [Preparation of PHJ Film] (Preparation Example 1) Ink (I-1) was applied to a cleaned glass substrate by spin coating to form a coating film, which was then heat-treated and dried for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heat-treated for 10 minutes at 100°C on a hot plate in the atmosphere (post-bake step) to form a first layer. Next, ink (I-5) was applied to the prepared first layer by spin coating to form a coating film, which was then heat-treated and dried for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heat-treated for 10 minutes at 100°C on a hot plate in the atmosphere (post-bake step) to form a second layer, thereby preparing a PHJ film (active layer).

[0454] (Preparation Examples 2 to 23 and 49) PHJ films (active layers) were prepared in the same manner as in Preparation Example 1 using inks (I-1) to (I-13), (I-18), and (I-36), except that they were used in the combinations shown in Table 8 below. Preparation Example 12 is a PHJ film in which a single film of an n-type semiconductor material was provided on a BHJ film.

[0455]

[0456] [Preparation of BHJ film] (Preparation Example 24) Ink (I-14) was applied to a cleaned glass substrate by spin coating to form a coating film, which was then dried by heat treatment for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heated on a hot plate at 100°C in the atmosphere for 10 minutes (post-bake step) to prepare a BHJ film.

[0457] (Preparation Examples 25 to 45 and 50) BHJ films were prepared as Preparation Examples 25 to 45 and 50 using inks (I-15) to (I-35) and (I-37) in the same manner as in Preparation Example 24, except that the combinations shown in Table 9 below were used.

[0458]

[0459] [Preparation of a Single Film of n-Type Semiconductor Material] (Preparation Example 46) Ink (I-5) was applied to a cleaned glass substrate by spin coating to form a coating film, which was then dried by heating for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heated for 10 minutes at 100°C on a hot plate in the atmosphere (post-bake step) to form a single film of n-type semiconductor material.

[0460] Preparation Examples 47 to 48 Inks (I-6) to (I-7) were used in the same manner as in Preparation Example 46, except that the combinations shown in Table 10 below were used, to form single films of n-type semiconductor material in Preparation Examples 47 to 48.

[0461]

[0462] <Production of Photoelectric Conversion Element and Sealed Body Thereof> (Photoelectric Conversion Element and Sealed Body Thereof Based on Preparation Example 1) A glass substrate on which a thin film of ITO (anode) was formed to a thickness of 45 nm by sputtering was prepared, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

[0463] Next, ink (I-1) was applied to an ITO substrate by spin coating to form a coating film, which was then dried by heating for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heated for 10 minutes at 100°C on a hot plate in the atmosphere (post-bake step) to form a first layer. Next, ink (I-5) was applied to the first layer by spin coating to form a coating film, which was then dried by heating for 5 minutes using a hot plate heated to 70°C in the atmosphere (pre-bake step), and then heated for 10 minutes at 100°C on a hot plate in the atmosphere (post-bake step) to form a second layer. Next, a zinc oxide dispersion (Avantama, product name N-10) was applied to the formed active layer by spin coating to form a coating film, which was then placed on a hot plate and dried in the atmosphere at 70°C for 2 minutes, forming an electron transport layer. Next, a silver (Ag) layer was formed to a thickness of about 60 nm on the formed hole transport layer to serve as a cathode. Through the above steps, a photoelectric conversion element was manufactured on the glass substrate, which included an anode provided in contact with the substrate, an active layer provided in contact with the anode, an electron transport layer provided in contact with the active layer, and a cathode provided in contact with the electron transport layer.

[0464] Next, a UV-curable sealant was applied to the outer periphery of a glass substrate serving as a sealing substrate, and the glass substrate serving as a sealing substrate was attached to the center of the glass substrate serving as a support substrate. After that, 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 × 2 mm square.

[0465] Similarly, a photoelectric conversion element and a sealed body thereof were produced based on Preparation Example 2 or Preparation Example 3, respectively.

[0466] [Evaluation of Photoelectric Conversion Device] (Evaluation of Dark Current (Jd)) For the sealed bodies based on Preparation Examples 1 to 3 manufactured as described above, the operation of the OPD was confirmed from the shape of the IV curve measured using a known method in a dark state where no light was irradiated. As shown in Table 11, the OPDs could be operated in Preparation Examples 1 to 3.

[0467] (Measurement of Wavelength Band (FW90%M) That Can Be Detected with High Sensitivity) The optical absorption spectrum of a PHJ film or BHJ film on a glass substrate was measured using a UV-Visible-Near-Infrared Spectrophotometer V-670 (manufactured by JASCO Corporation). The wavelength range that satisfies 90% or more of the absorbance at the maximum absorption wavelength position at the absorption peak of the obtained spectrum was determined as FW90%M (Full Width at 90% of the Maximum). FW90%M is a numerical value that indicates the spread of the distribution that monotonically decreases around the maximum value, and is the distance (unit: nm) between the positions indicated by 90% of the maximum value on both sides of the maximum value. In the present disclosure, a larger value of FW90%M indicates a wider wavelength band that can be detected with high sensitivity. Note that in the present disclosure, the maximum value is the maximum value that exists beyond 1000 nm in the optical absorption spectrum. Furthermore, if there are multiple maximum values ​​in the range exceeding 1000 nm in the optical absorption spectrum, the largest FW90%M value is adopted as the FW90%M value.

[0468] (FW90%M Ratio) From the FW90%M values ​​obtained for the PHJ film, BHJ film, or n-type monolayer film, the FW90%M ratio of the PHJ to the BHJ or the FW90%M ratio of the PHJ to the n-type monolayer film was calculated. As shown in Tables 11 and 12, the PHJ films of Preparation Examples 1 to 12 and 49 all had FW90%M ratios greater than 1.00, i.e., the wavelength band that could be detected with high sensitivity was wider than that of the BHJ film or n-type monolayer film.

[0469] (Measurement of Maximum Light Absorption Wavelength (λmax) of Active Layer) The maximum light absorption wavelength (λmax) of the active layer was measured by the method described above. As shown in Tables 11 and 12, in Preparation Examples 1 to 12 and 49, the λmax of the active layer exceeded 1,000 nm.

[0470] (Measurement of Optical Absorption Edge Wavelength (λth) of Active Layer) The optical absorption edge wavelength (λth) of the active layer was measured by the method described above.

[0471]

[0472]

[0473] (Calculation of Energy Band Gap (Eg)) The energy band gap (Eg) was calculated using the optical absorption edge wavelength (λth) of the semiconductor material contained in the active layer according to the following formula: Energy band gap (Eg) = hc / optical absorption edge wavelength (Planck's constant h = 6.626 × 10 -34 Js, speed of light c=3×10 8 m / s)

[0474] The HOMO energy value was measured by ultraviolet photoelectron spectroscopy (UPS), which can be performed in air using a photoelectron spectrometer.

[0475] (1) UPS Sample Preparation First, compounds P-1 to P-4 and compounds N-1 to N-9 were each dissolved in chloroform to obtain a solution. Next, each of the obtained solutions was applied to a glass substrate by spin coating to form a coating film, which was then dried on a hot plate at 70°C to form a 100 nm thick layer, which was used as a sample. Compound N-10 was similarly dissolved in a mixed solvent of 1,2,4-trimethylbenzene and 1,2-dimethoxybenzene (mixing ratio: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90% by mass / 10% by mass), and the solution was applied to a glass substrate by spin coating to form a coating film, which was then dried on a hot plate at 70°C to form a 80 nm thick layer, which was used as a sample.

[0476] (2) Measurement of HOMO Energy by UPS Method Based on the number of electrons measured for each of the obtained samples by the UPS method using a photoelectron spectrometer (Model AC-2, manufactured by Riken Keiki Co., Ltd.) in air, the HOMO energy of each of Compounds P-1 to P-4 and Compounds N-1 to N-10 was calculated. Here, the UPS method is a method for measuring the number of photoelectrons emitted in response to the energy of ultraviolet light irradiated onto a solid surface. From the minimum energy at which photoelectrons are generated, the work function can be estimated if the sample is a metal, or the HOMO energy can be estimated if the sample is a semiconductor material.

[0477] The LUMO energy of each of Compounds P-1 to P-4 and Compounds N-1 to N-10 was calculated by the following formula: LUMO energy = energy band gap (Eg) - HOMO energy Band gap (Eg) = hc / optical absorption end wavelength Where, Planck's constant h = 6.626 × 10 -34 Js, speed of light c=3×10 8 m / s.

[0478]

[0479] As described above, the present disclosure provides a photoelectric conversion element and an optical sensor that can detect light in a wide wavelength range with high sensitivity in the long wavelength range.

[0480] REFERENCE SIGNS LIST 10 Photoelectric conversion element 11 Support substrate 12 Anode 13 Hole transport layer 14 First layer 15 Second layer 16 Electron transport layer 17 Cathode 18 Sealing member 19 Active layer

Claims

1. A photoelectric conversion device having an anode, a cathode, and an active layer existing between the anode and the cathode, wherein the active layer has at least a first layer containing either a p-type semiconductor material or an n-type semiconductor material, and a second layer containing a semiconductor material of a type different from the semiconductor material contained in the first layer, and the maximum light absorption wavelength (λmax) of the active layer exceeds 1000 nm.

2. The photoelectric conversion device according to claim 1, wherein the light absorption end wavelength (λth) of the active layer is 1200 nm or more.

3. The photoelectric conversion device according to claim 1 or claim 2, wherein the p-type semiconductor material or the n-type semiconductor material contained in the first layer has an energy band gap of less than 1 eV.

4. The photoelectric conversion device according to claim 1 or claim 2, wherein the semiconductor material contained in the first layer is an n-type semiconductor material.

5. The photoelectric conversion device according to claim 1 or claim 2, wherein the semiconductor material contained in the first layer is an n-type semiconductor material, and the LUMO energy of the n-type semiconductor material is -4.2 eV or less.

6. The photoelectric conversion device according to claim 1 or claim 2, wherein the semiconductor material contained in the first layer is an n-type semiconductor material, and the HOMO energy of the n-type semiconductor material is -5.0 eV or less.

7. The optoelectronic conversion element according to claim 1 or claim 2, wherein the semiconductor material contained in the first layer is an n-type semiconductor material, and the n-type semiconductor material is a compound represented by the following formula (1). (In formula (1), D is an electron-donating divalent group and has at least one monovalent side chain R Ｄ１ ; L1 is a divalent aromatic group and has at least one monovalent side chain R Ｌ１ ; the aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit; R Ｄ１ and R Ｌ１ are each independently a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substitutedoxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group; L2 is a divalent aromatic group; m is an integer of 1 to 4; n is an integer of 0 to 4; A1 and A2 are each independently a group represented by the following formula (A-1). In formula (A-1), Ar represents a carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent, the carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a condensed ring, and when the carbocyclic ring or the heterocyclic ring has a plurality of substituents, the plurality of substituents may be the same or different.) 8. The photoelectric conversion device according to claim 7, wherein n is an integer of any one of 1 to 4.

9. The photoelectric conversion device according to claim 1 or claim 2, wherein the first layer is in contact with a second layer containing a p-type semiconductor material and an n-type semiconductor material.

10. The photoelectric conversion device according to claim 1 or claim 2, wherein the second layer contains a p-type semiconductor material, and the p-type semiconductor material is a hole transport material.

11. The second layer contains a p-type semiconductor material, and the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The photoelectric conversion element according to claim 1 or claim 2. (In formula (3), Ar ３ and Ar ４ each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any group represented by the following formula (Z-1) to formula (Z-7). In formulas (Z-1) to (Z-7), R each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substitutedoxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group, and in each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different from each other. In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.) 12. The photoelectric conversion device according to claim 1 or claim 2, which is a photodetector.

13. An optical sensor including the photoelectric conversion device according to claim 12.

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