Composition, film, organic photoelectric conversion element, and light detection element

Abstract

The present application addresses the problem of providing a composition capable of producing an active layer of a photoelectric conversion element in which dark current is reduced. The present invention relates to a composition containing a p-type semiconductor, an n-type semiconductor, a surfactant and a solvent. A film containing a p-type semiconductor, an n-type semiconductor, and a surfactant. And an organic photoelectric conversion element comprising a first electrode, the film, and a second electrode in this order. And a light detection element comprising the organic photoelectric conversion element.

Description

Technical Field

[0001] The present invention relates to a composition, a film, an organic photoelectric conversion element, and a light detection element. Background Art

[0002] In recent years, organic photoelectric conversion elements containing an organic compound in an active layer have attracted attention, and attempts have been made to improve the characteristics of light detection elements containing such organic photoelectric conversion elements (see Non-Patent Document 1). Prior art literature Non-patent literature

[0003] Non-patent literature 1: Yazhong Wang, et al., Mater. Horiz., 2022, 9, 220-251 Summary of the invention Problem that the invention aims to solve

[0004] The current (dark current) flowing in the dark state of the photoelectric conversion element contained in the light detection element is preferably small. Therefore, there is a need for a composition that can manufacture an active layer of a photoelectric conversion element that reduces dark current; a film that can function as an active layer of a photoelectric conversion element that reduces dark current; an organic photoelectric conversion element containing the film; and a light detection element that reduces dark current containing the organic photoelectric conversion element. Technical means of solving problems

[0005] The inventors have conducted intensive research to solve the above-mentioned problems, thereby completing the present invention. The present invention provides the following contents.

[0006] [1] A composition comprising a p-type semiconductor, an n-type semiconductor, a surfactant and a solvent. [2] The composition according to [1], wherein the p-type semiconductor is a polymer compound having a donor-acceptor structure. [3] The composition according to [1] or [2], wherein the p-type semiconductor is a polymer compound comprising one or more structural units selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). [Chemistry 1] (In formula (I), Ar 1 and Ar 2 Each independently represents a trivalent aromatic heterocyclic group which may have a substituent, Z represents a group represented by any one of the following formulae (Z-1) to (Z-7). [Chemistry 2] (In formulae (Z-1) to (Z-7), 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 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, an aryl group which may have a substituent, an alkoxy 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 imide residue which may have a substituent, an amide group which may have a substituent, an imide group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a cyano group, a nitro group, -C(=O)-R c The group represented by -SO2-R d The group represented by R c and R d Each independently represents a hydrogen 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 alkoxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. In formula (Z-1) to formula (Z-7), when there are two Rs, the two Rs may be the same or different. [Chemistry 3] (In formula (II), Ar 3 represents a divalent aromatic heterocyclic group. ) [4] The composition according to any one of [1] to [3], wherein the n-type semiconductor is a fullerene derivative. [5] The composition according to any one of [1] to [3], wherein the n-type semiconductor is a non-fullerene compound. [6] The composition according to any one of [1] to [5], wherein the solvent contains an aromatic hydrocarbon solvent. [7] The composition according to any one of [1] to [6], wherein the surfactant is a nonionic surfactant. [8] The composition according to any one of [1] to [7], wherein the surfactant is a compound having a poly(meth)acrylate structure. [9] The composition according to any one of [1] to [8], wherein the surfactant is a compound having an organopolysiloxane structure.

[10] The composition according to any one of [1] to [9], wherein the surfactant is a fluorine-based surfactant.

[11] A film comprising a p-type semiconductor, an n-type semiconductor, and a surfactant.

[12] An organic photoelectric conversion element comprising, in order, a first electrode, the film described in

[11] , and a second electrode.

[13] A light detection element comprising the organic photoelectric conversion element described in

[12] . Effects of the Invention

[0007] According to the present invention, there can be provided a composition for manufacturing an active layer of a photoelectric conversion element for reducing dark current; a film that can function as an active layer of a photoelectric conversion element for reducing dark current; an organic photoelectric conversion element containing the film; and a light detection element for reducing dark current containing the organic photoelectric conversion element. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] [ Figure 1 ] Figure 1 This is a diagram schematically showing a configuration example of a photoelectric conversion element. Explanation of symbols 10 photoelectric conversion element 11 supporting substrate 12 first electrode 13 first intermediate layer 14 active layer 15 second intermediate layer 16 second electrode 17 packaging component DETAILED DESCRIPTION

[0009] The following describes the embodiments of the present invention with reference to the accompanying drawings. In addition, the accompanying drawings are only to roughly represent the shapes, sizes and configurations of the constituent elements to the extent that the invention can be understood. The present invention is not limited to the following description, and each constituent element can be appropriately changed within the scope of the present invention. In the drawings used in the following description, the same constituent elements are represented by the same symbols, and repeated descriptions are omitted. In addition, the structure of the embodiments of the present invention is not necessarily limited to being used in accordance with the configuration of the illustrated examples. The constituent elements of the embodiments shown below can be appropriately combined.

[0010] [1. Explanation of common terms] In this specification, a "polymer compound" refers to a polymer having a molecular weight distribution, and the number average molecular weight converted to polystyrene is 1×10 3 Above 1×10 8 The following polymers: The total amount of the structural units contained in the polymer compound is 100 mol%.

[0011] In this specification, "structural unit" refers to one or more units present in a polymer compound. "Monomer unit" refers to a unit having a structure that can be obtained by polymerizing the monomer. "Monomer unit" is not limited by its production method.

[0012] In the present specification, the "hydrogen atom" may be a light hydrogen atom or a heavy hydrogen atom.

[0013] In the present specification, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0014] The embodiment of “optionally having a substituent” includes two aspects: a case where all hydrogen atoms constituting the compound or group are unsubstituted and a case where part or all of one or more hydrogen atoms are substituted with a substituent.

[0015] 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 alkoxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a hydroxyl group, a carboxyl group, a substituted amino group, an acyl group, an imide residue, an amide group, an imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group.

[0016] In the present specification, "alkyl" may have a substituent. Unless otherwise specified, "alkyl" may be any one of linear and branched. The number of carbon atoms of a linear alkyl group, not including the number of carbon atoms of the substituent, is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20. The number of carbon atoms of a branched or cyclic alkyl group, not including the number of carbon atoms of the substituent, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.

[0017] Specific examples of the alkyl group include unsubstituted groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-ethylbutyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 3-n-propylheptyl, n-decyl, 3,7-dimethyloctyl, 2-ethyloctyl, 2-n-hexyldecyl, n-dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl; and substituted alkyl groups such as trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, 3-phenylpropyl, 3-(4-methylphenyl)propyl, 3-(3,5-di-n-hexylphenyl)propyl, 6-ethyloxyhexyl, cyclohexylmethyl, and cyclohexylethyl.

[0018] The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms of the cycloalkyl group excluding the number of carbon atoms of the substituent is usually 3 to 30, preferably 3 to 20.

[0019] Examples of the cycloalkyl group include unsubstituted alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and adamantyl, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkoxy groups, aryl groups and fluorine atoms.

[0020] Specific examples of the cycloalkyl group having a substituent include a methylcyclohexyl group and an ethylcyclohexyl group.

[0021] The "alkenyl group" may be linear or branched. The alkenyl group may have a substituent. The number of carbon atoms in the alkenyl group excluding the number of carbon atoms in the substituent is usually 2 to 30, preferably 2 to 20.

[0022] Examples of alkenyl groups include unsubstituted alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl and 7-octenyl, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkoxy groups, aryl groups and fluorine atoms.

[0023] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group excluding the number of carbon atoms of the substituent is usually 3 to 30, preferably 3 to 20.

[0024] Examples of the cycloalkenyl group include unsubstituted cycloalkenyl groups such as cyclohexenyl groups, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkoxy groups, aryl groups, and fluorine atoms.

[0025] Examples of the cycloalkenyl group having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0026] The "alkynyl group" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms in the alkynyl group excluding the number of carbon atoms in the substituent is usually 2 to 30, preferably 2 to 20.

[0027] Examples of the alkynyl group include alkynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 5-hexynyl and other alkynyl groups having no substituent, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkoxy groups, aryl groups and fluorine atoms.

[0028] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms of the cycloalkynyl group excluding the number of carbon atoms of the substituent is usually 4 to 30, preferably 4 to 20.

[0029] Examples of the cycloalkynyl group include cycloalkynyl groups having no substituent such as cyclohexynyl group, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkoxy groups, aryl groups, and fluorine atoms.

[0030] Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0031] The "alkoxy group" may be linear or branched. The alkoxy group may have a substituent. The number of carbon atoms in the alkoxy group excluding the number of carbon atoms in the substituent is usually 1 to 30, preferably 1 to 20.

[0032] Examples of the alkoxy group include alkoxy groups having no substituent such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyloctyloxy, 3-heptyldodecyloxy and lauryloxy, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkoxy groups, aryl groups and fluorine atoms.

[0033] The cycloalkyl group in the "cycloalkoxy group" may be a monocyclic group or a polycyclic group. The cycloalkoxy group may have a substituent. The number of carbon atoms in the cycloalkoxy group excluding the number of carbon atoms in the substituent is usually 3 to 30, preferably 3 to 20.

[0034] Examples of the cycloalkoxy group include unsubstituted cycloalkoxy groups such as cyclopentyloxy groups, cyclohexyloxy groups, and cycloheptyloxy groups, and groups in which hydrogen atoms in these groups are substituted with substituents such as fluorine atoms and alkyl groups.

[0035] The "alkylthio group" may be linear or branched. The alkylthio group may have a substituent. The number of carbon atoms in the alkylthio group excluding the number of carbon atoms in the substituent is usually 1 to 30, preferably 1 to 20.

[0036] Examples of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a tert-butylthio group, an n-pentylthio group, an n-hexylthio group, an n-heptylthio group, an n-octylthio group, a 2-methylhexylthio group, an n-nonylthio group, an n-decylthio group, a 3,7-dimethyloctylthio group, a 3-heptyldodecylthio group, a laurylthio group and a trifluoromethylthio group.

[0037] 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 excluding the number of carbon atoms in the substituent is usually 3 to 30, preferably 3 to 20.

[0038] As an example of the cycloalkylthio group which may have a substituent, a cyclohexylthio group can be mentioned.

[0039] "p-valent aromatic carbocyclic group" refers to the atomic group remaining after removing p hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon that may have a substituent. Aromatic hydrocarbons also include compounds having condensed rings, and compounds in which two or more selected from the group consisting of independent benzene rings and condensed rings are directly bonded or bonded through a divalent group such as vinylidene. The p-valent aromatic carbocyclic group may further have a substituent.

[0040] The "aryl group" refers to a monovalent aromatic carbocyclic group. The aryl group may have a substituent. The number of carbon atoms in the aryl group excluding the number of carbon atoms in the substituent is usually 6 to 60, preferably 6 to 48.

[0041] Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl and other aryl groups having no substituents, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkoxy groups, aryl groups and fluorine atoms.

[0042] The "aryloxy group" may have a substituent. The aryloxy group generally has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, excluding the carbon atoms of the substituent.

[0043] Examples of the aryloxy group include unsubstituted aryloxy groups such as phenoxy, 1-naphthyloxy, 2-naphthyloxy, 1-anthryloxy, 9-anthryloxy and 1-pyreneoxy groups, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkoxy groups and fluorine atoms.

[0044] The "arylthio group" may have a substituent. The arylthio group has generally 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, excluding the carbon atoms of the substituent.

[0045] Examples of arylthio groups which may have a substituent include phenylthio, C1-C12 alkoxyphenylthio, C1-C12 alkylphenylthio, 1-naphthylthio, 2-naphthylthio and pentafluorophenylthio. "C1-C12" means that the number of carbon atoms of the group immediately following it is 1 to 12. Furthermore, "Cm-Cn" means that the number of carbon atoms of the group immediately following it is m to n. The same applies below.

[0046] A "p-valent heterocyclic group" (p represents an integer greater than 1) refers to an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting a ring from a heterocyclic compound that may have a substituent. A "p-valent heterocyclic group" includes a "p-valent aromatic heterocyclic group". A "p-valent aromatic heterocyclic group" refers to an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting a ring from an aromatic heterocyclic compound that may have a substituent.

[0047] The aromatic heterocyclic compound includes not only compounds in which the heterocycle itself exhibits aromaticity but also compounds in which an aromatic ring is fused to the heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0048] Specific examples of aromatic heterocyclic compounds in which the heterocyclic ring itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole and dibenzophosphole.

[0049] Specific examples of aromatic heterocyclic compounds in which the heterocyclic ring itself does not exhibit aromaticity but an aromatic ring is condensed in the heterocyclic ring include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole and benzopyran.

[0050] The p-valent heterocyclic group may have a substituent. The p-valent heterocyclic group generally has 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms, excluding the carbon atoms of the substituent.

[0051] Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (e.g., thienyl, pyrrolyl, furyl, pyridyl, quinolyl, isoquinolyl, pyrimidinyl, triazinyl), monovalent non-aromatic heterocyclic groups (e.g., piperidinyl, piperazinyl), and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkoxy groups, and fluorine atoms.

[0052] The "substituted amino group" refers to an amino group having a substituent. The substituent of the amino group is preferably an alkyl group, a cycloalkyl group, an aryl group, and a monovalent heterocyclic group. The substituted amino group usually has 2 to 30 carbon atoms excluding the carbon atoms of the substituent.

[0053] Examples of the substituted amino group include dialkylamino (e.g., dimethylamino, diethylamino), and diarylamino (e.g., diphenylamino, bis(4-methylphenyl)amino, bis(4-tert-butylphenyl)amino, and bis(3,5-di-tert-butylphenyl)amino).

[0054] The "acyl group" may have a substituent. The number of carbon atoms of the acyl group excluding the number of carbon atoms of the substituent is usually 2 to 20, preferably 2 to 18. Specific examples of the acyl group include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl and pentafluorobenzoyl.

[0055] "Imine residue" refers to an atomic group remaining after removing a hydrogen atom directly bonded to a carbon atom or a nitrogen atom constituting a carbon-nitrogen double bond from an imine compound. "Imine compound" refers to an organic compound having a carbon-nitrogen double bond in the molecule. Examples of imine compounds include aldimine, ketimines, and compounds in which the hydrogen atom bonded to the nitrogen atom constituting the carbon-nitrogen double bond in aldimine is substituted with a substituent such as an alkyl group or a cycloalkyl group.

[0056] The number of carbon atoms in the imine residue is usually 2 to 20, preferably 2 to 18. Examples of the imine residue include groups represented by the following structural formulas.

[0057] [Chemistry 4]

[0058] "Acylamide" 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 an amide is usually about 1 to 20, preferably 1 to 18. Specific examples of amide include formamide, acetamide, propionamide, butyramide, benzamide, trifluoroacetamide, pentafluorobenzamide, diformamide, diacetamide, dipropionamide, dibutyramide, dibenzamide, di(trifluoroacetamide) and di(pentafluorobenzamide).

[0059] The "acylimido group" refers to an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an imide. The number of carbon atoms in the acylimido group is usually 4 to 20. Specific examples of the acylimido group include the following groups.

[0060] [Chemistry 5]

[0061] The "substituted oxycarbonyl group" refers to a group represented by R'-O-(C=O)-, wherein R' represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and these groups may have a substituent. The substituted oxycarbonyl group usually has 2 to 60 carbon atoms, and preferably has 2 to 48 carbon atoms.

[0062] Specific examples of the substituted oxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, 3,7-dimethyloctyloxycarbonyl, dodecyloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthoxycarbonyl and pyridyloxycarbonyl.

[0063] The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms of the alkylsulfonyl group excluding the number of carbon atoms of the substituent is usually 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0064] The “*” in a chemical formula represents an atomic bond.

[0065] A "π-conjugated system" refers to a system in which π electrons are delocalized across multiple bonds.

[0066] The term "(meth)acrylic acid" includes acrylic acid, methacrylic acid and a combination thereof.

[0067] The term "(meth)acrylate" includes acrylate, methacrylate and a combination thereof.

[0068] In the chemical formula, "Me" represents a methyl group, "Et" represents an ethyl group, and "Bu" represents a butyl group.

[0069] The "solvent" may be a dispersion solvent.

[0070] [2. Composition] The composition according to one embodiment of the present invention comprises a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent. In addition to the p-type semiconductor, the n-type semiconductor, the surfactant, and the solvent, the composition may contain any component as required.

[0071] The composition may be a solution, or may be a dispersion such as a dispersion, an emulsion, or a suspension.

[0072] The dark current of a photoelectric conversion element including a film produced from the composition of this embodiment is reduced.

[0073] [2.1. Surfactants] Surfactants are substances that change the surface properties by addition. Surfactants usually have a hydrophilic group and a hydrophobic group in one molecule.

[0074] When the composition according to the present embodiment contains a surfactant, the dark current of a photoelectric conversion element including a film obtained from the composition can be effectively reduced.

[0075] The reason why the composition of the present embodiment can effectively reduce the dark current of the photoelectric conversion element by containing the surfactant is presumed as follows without limiting the present invention.

[0076] Usually, the coating composition is applied to the coating object such as an electrode and an intermediate layer to form a coating film, and the coating film is further dried to form a film (active layer). It is believed that the surfactant exists in a film-like state on the coating film surface. When the coating film is dried, it is believed that the surfactant unevenly distributed on the coating film surface directly segregates and solidifies. It is believed that as a result, there is a surfactant film on the surface of the obtained film (active layer), which functions as an insulating layer, thereby reducing the dark current of the photoelectric conversion element.

[0077] Furthermore, it is considered that the phase separation structure formed by the p-type semiconductor and the n-type semiconductor also changes due to the action of the surfactant, and that the dark current of the photoelectric conversion element can be reduced by this change.

[0078] As a surfactant that can effectively reduce the dark current of a photoelectric conversion element including a film made of the composition according to this embodiment, an appropriate surfactant can be selected by appropriately selecting the types of the hydrophilic group and the hydrophobic group in the molecule.

[0079] Among the surfactants contained in the composition of the present embodiment, when selecting based on the type of hydrophilic group, it is preferred to use a surfactant classified as nonionic. Among the solvents contained in the composition of the present embodiment, non-aqueous solvents such as aromatic hydrocarbon solvents can be used. Nonionic surfactants are also preferred from the perspective of excellent solubility in solvents. As examples of hydrophilic groups, groups having epoxy groups such as ethylene oxide and propylene oxide, amino groups, keto groups, carboxyl groups, sulfonic groups, etc. can be cited. The surfactant can have one or more groups selected therefrom as the hydrophilic group.

[0080] Among the surfactants contained in the composition of this embodiment, when selected based on the type of hydrophobic group, there can be mentioned: acrylic surfactants having a poly(meth)acrylate structure in the hydrophobic group, silicone surfactants having an organopolysiloxane structure, and fluorine-based surfactants in which some or all of the hydrogen atoms in these groups are substituted with fluorine atoms.

[0081] In one embodiment, the surfactant preferably has a poly(meth)acrylate structure. Wherein, the poly(meth)acrylate structure is a structure represented by the following formula (SF-1). By having a poly(meth)acrylate structure, the composition can effectively reduce the dark current of the photoelectric conversion element. In addition to the poly(meth)acrylate structure, the surfactant may also contain any structural unit. The surfactant having a poly(meth)acrylate structure may be an oligomer or a polymer.

[0082] [Chemistry 6]

[0083] In formula (SF-1), the presence of multiple R sf1 Each independently represents a hydrogen atom or a methyl group. The existence of multiple R sf2 Each independently represents an organic group. sf2 Two or more of them may together form a cross-linking group. Preferably, R sf2Each independently represents an alkyl group, a cycloalkyl group, an alkoxyalkyl group, a group having a polyoxyalkylene group, an aryl group, an arylalkyl group, or an aryloxyalkyl group, and these groups may further have a substituent (for example, a fluorine atom). As R sf2 Preferred specific examples of the alkyl group represented by include fluorine-substituted alkyl groups in which some of the hydrogen atoms in the alkyl group are substituted with fluorine atoms (for example, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,4,4-hexafluorobutyl, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl, 1,1-dimethyl-2,2,3,3-pentafluoropropyl, 2-(perfluoropropyl)ethyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl, Methyl-2,2,3,3,4,4-hexafluorobutyl, 1,1-dimethyl-2,2,3,3,4,4,4-heptafluorobutyl, 2-(perfluorobutyl)ethyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, perfluoropentylmethyl, 1,1-dimethyl-2,2,3,3,4,4,5,5-octafluoropentyl, 1,1-dimethyl-2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2-(perfluoropentyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl , perfluorohexylmethyl, 2-(perfluorohexyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-tetradecafluorooctyl, perfluoroheptylmethyl, 2-(perfluoroheptyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecanoyl, perfluorooctylmethyl, 2-(perfluorooctyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecanoyl, perfluorononylmethyl, 2,2,3,4,4,4- hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl), a fluorine atom-substituted alkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms (perfluoroalkyl group) (for example, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, nonafluoro-n-butyl, nonafluoro-isobutyl, nonafluoro-sec-butyl, nonafluoro-tert-butyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl).

[0084] In formula (SF-1), n ​​(number of repeating units) is, for example, 2 or more, 3 or more, 4 or more, 5 or more, or 10 or more, and for example, 3000 or less.

[0085] As the surfactant having a poly(meth)acrylate structure, a commercially available product can be used. Examples of commercially available nonionic surfactants having a poly(meth)acrylate structure include: "F-556", "R-40", "MEGAFACE F-110", "MEGAFACE F-113", "MEGAFACE F-120", "MEGAFACE F-812", "MEGAFACE F-142D", "MEGAFACE F-144D", "MEGAFACE F-150", "MEGAFACE F-171", "MEGAFACE F-173", "MEGAFACE F-177", "MEGAFACE F-183", "MEGAFACE F-195", "MEGAFACE F-824", "MEGAFACE F-833", "MEGAFACE F-114", "MEGAFACE F-410", "MEGAFACE F-493", "MEGAFACE F-494", "MEGAFACE F-443", "MEGAFACE F-444", "MEGAFACE F-445", "MEGAFACEF-446", "MEGAFACE F-470", "MEGAFACE F-471", "MEGAFACE F-474", "MEGAFACE F-475", "MEGAFACE F-477", "MEGAFACE F-478", "MEGAFACE F-479", "MEGAFACE "MEGAFACE F-483", "MEGAFACE F-484", "MEGAFACE F-486", "MEGAFACEF-487", "MEGAFACE F-489", "MEGAFACE F-172D", "MEGAFACE F-178K", ​​"MEGAFACE F-178RM", "MEGAFACE R-08", "MEGAFACE R-30", "MEGAFACE F-472SF", "MEGAFACE BL-20", "MEGAFACE R-61", "MEGAFACE R-90", "MEGAFACE ESM-1", "MEGAFACE MCF-350SF" (all manufactured by DIC Corporation), "FUTagent 100", "FUTagent 100C", "FUTagent 110", "FUTagent 150", "FUTagent 150CH", "FUTagent A", "FUTagent 100A-K", "FUTagent501, FUTagent300, FUTagent 310, FUTagent 320, FUTagent400SW, FTX-400P, FUTagent 251, FUTagent 215M, FUTagent 212MH, FUTagent 250, FUTagent 222F","FUTagent212D","FTX-218","FTX-209F","FTX-213F","FTX-233F","FUTagent 245F", "FTX-208G", "FTX-240G", "FTX-206D", "FTX-220D", "FTX-230D", "FTX-240D", "FTX-207S", "FTX-211S", "FTX-220S", "FTX-230S", "FTX-750FM", "FTX-730FM", "FTX-730FL" , “FTX-710FS”, “FTX-710FM”, “FTX-710FL”, “FTX-750LL”, “FTX-730LS”, “FTX-730LM”, “FTX-730LL”, “FTX-710LL” (above manufactured by NEOS Corporation), “BYK-300”, “BYK-302”, “BYK-306”, “BYK-307”, BYK-310,BYK-315,BYK-320,BYK-322,BYK-323,BYK-325,BYK-330,BYK-331,BYK-333,BYK-337,BYK-340,BYK-344,BYK-370,BYK-375,BYK-377,B YK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-357, BYK-390, BYK-392, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-Silclean 3700(manufactured by BYK Japan Corporation), TEGO Rad2100, TEGO Rad2200 N, TEGO Rad2250, TEGO Rad2300, TEGO Rad2500, TEGO Rad2600, TEGO Rad2700 (manufactured by Evonik Industries Corporation).

[0086] In one embodiment, the surfactant preferably has an organopolysiloxane structure. Wherein, the organopolysiloxane structure is a structure represented by the following formula (SF-2). By having an organopolysiloxane structure, the composition can effectively reduce the dark current of the photoelectric conversion element. In addition to the organopolysiloxane structure, the surfactant can also contain any structural unit. The surfactant having an organopolysiloxane structure can be an oligomer or a polymer.

[0087] [Chemistry 7]

[0088] In formula (SF-2), the presence of multiple R sf3 Each independently represents an organic group. Preferably, R sf3 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, a group having a polyoxyalkylene group, or a group having a structure represented by -(C=O)-O- (for example, a group having one or more, two or more, or three or more structures represented by -(C=O)-O-), and these groups may have a substituent.

[0089] The surfactant having an organopolysiloxane structure may have any terminal group. Examples of terminal groups that the surfactant having an organopolysiloxane structure may have include alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, groups having polyoxyalkylene groups, aryl groups, arylalkyl groups, and poly(meth)acryloyl groups. These groups may also contain substituents (e.g., fluorine atoms).

[0090] In formula (SF-2), the range of n (number of repeating units) is, for example, 2 or more, 3 or more, 4 or more, 5 or more, or 10 or more, and is, for example, 3000 or less.

[0091] As the surfactant having an organopolysiloxane structure, a commercially available product can be used. Examples of commercially available nonionic surfactants having an organopolysiloxane structure include: BYK-300, BYK-301 / 302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-338, BYK-339, BYK-400, BYK-401, BYK-402, BYK-403, BYK-404, BYK-405, BYK-406, BYK-407, BYK-408, BYK-409, BYK-410, BYK-411, BYK-412, BYK-413, BYK-414, BYK-415, BYK-416, BYK-417, BYK-418, BYK-419, BYK-420, BYK-421, BYK-422, BYK-423, BYK-425, BYK-426 -341", "BYK-344", "BYK-345 / 346", "BYK-347", "BYK-348", "BYK-349", "BYK-370", "BYK-375", "BYK-377", "BYK-37 8", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (the above is BYK Japan Co., Ltd.), trade names "AC FS180", "AC FS 360", "AC S20" (all manufactured by Algin Chemie), trade names "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", "PolyflowKL-700" (all manufactured by Kyoeisha Chemical Co., Ltd.), trade names "KP-301", "KP-306", "KP-109", "KP-310", "KP-310B", "KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112", "KP-360A", "KP-361", "KP-354", "KP-355", "KP-356", "KP-357", "KP-358", "KP-359", "KP-362", "KP-365", "KP-366", "KP-368", "KP-3 "69", "KP-330", "KP-620", "KP-625", "KP-650", "KP-651", "KP-390", "KP-391", "KP-392" (all manufactured by Shin-Etsu Chemical Co., Ltd.), trade names "LP-7001", "LP-7002", "SH28PA", "8032ADDITIVE", "57ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67ADDITIVE", "8618ADDITIVE", "3ADDITIVE", "56ADDITIVE" (all manufactured by Dow Corning Toray Co., Ltd.), "TEGO WET 270" (manufactured by Evonik Degussa Japan Co., Ltd.), and "NBX-15" (manufactured by NEOS Co., Ltd.).

[0092] In one embodiment, the surfactant is preferably a fluorine-based surfactant. The fluorine-based surfactant refers to a surfactant containing fluorine atoms in its molecule. The composition can effectively reduce the dark current of the photoelectric conversion element by containing the fluorine-based surfactant.

[0093] As the fluorine-based surfactant, a commercially available product can be used. Examples of commercially available fluorine-based surfactants include: "F-556", "R-40", MEGAFACE F171, same brand F172, same brand F173, same brand F176, same brand F177, same brand F141, same brand F142, same brand F143, same brand F144, same brand R30, same brand F437, same brand F475, same brand F479, same brand F482, same brand F554, same brand F780, RS-72-K (all manufactured by DIC), Fluorad FC430, same brand FC431, same brand FC171, Novec FC4430, same brand FC4432 (all manufactured by 3M Japan), Surflon S-382, SC-101 of the same brand, SC-103 of the same brand, SC-104 of the same brand, SC-105 of the same brand, SC-1068 of the same brand, SC-381 of the same brand, SC-383 of the same brand, S-393 of the same brand, KH-40 of the same brand (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA).

[0094] (Properties) The surfactant is preferably a liquid at 25° C. and 1 atm. When the surfactant is a liquid at 25° C. and 1 atm, the surfactant has good solubility in the composition.

[0095] (Viscosity) The viscosity η of the surfactant is preferably 1 mPa·s or more, more preferably 10 mPa·s or more, further preferably 100 mPa·s or more, and preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less. When the viscosity η of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.

[0096] The viscosity η is a value measured by a rheometer at a temperature of 25° C. and a shear rate of 100 (1 / s).

[0097] (Molecular weight) The peak molecular weight Mp of the surfactant is preferably 100 or more, more preferably 1000 or more, and preferably 10,000 or less, more preferably 5,000 or less. When the peak molecular weight Mp of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.

[0098] The peak molecular weight Mp of the surfactant is a value measured by gel permeation chromatography (GPC). The peak molecular weight Mp may be a peak top value in a GPC chromatogram measured under the following measurement conditions.

[0099] As the mobile phase of GPC, o-dichlorobenzene was used at a flow rate of 1.0 mL / min. As the chromatographic column, Shodex KD-806M manufactured by Showa Denko K.K. was used, and as the guard column, Shodex KD-G manufactured by Showa Denko K.K. was used.

[0100] As detectors, a UV-vis detector (manufactured by Shimadzu Corporation, SPD-M20A) and a differential refractive index detector (manufactured by Shimadzu Corporation, RID-10A) were used.

[0101] The compound (polymer) to be measured was mixed with 1-chloronaphthalene as a solvent to a concentration of 0.05 mass %, and stirred at 80° C. for 2 hours to prepare a solution in which the compound (polymer) was dissolved.

[0102] 10 μL of the obtained solution was injected as a sample into the above-mentioned measuring device (GPC), and the peak molecular weight (Mp) was measured.

[0103] (Fluorine content) When the surfactant is a fluorine-based surfactant, the solid content of the fluorine-based surfactant excluding the solvent is 100% by mass, and the fluorine content of the surfactant is preferably 1% by mass or more, more preferably 5% by mass or more, and also preferably 50% by mass or less, more preferably 30% by mass or less. When the fluorine content of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced. When the fluorine content of the surfactant is below the above upper limit, the water repellency of the film (active film) obtained by the composition decreases, and an aqueous coating liquid can be easily applied to the film.

[0104] The fluorine content in the surfactant can be measured by combustion ion chromatography or the like.

[0105] (Content ratio of surfactant) The content of the surfactant in the composition is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, and is further preferably 1.0 mass % or less, more preferably 0.5 mass % or less, based on 100 mass % of the total mass of the solvent.

[0106] Based on the total mass of the n-type semiconductor, the p-type semiconductor and the surfactant as 100 mass%, the content ratio of the surfactant in the composition is preferably 0.1 mass% or more, more preferably 1 mass% or more, and further preferably 3 mass% or more. In addition, based on the total mass of the n-type semiconductor, the p-type semiconductor and the surfactant as 100 mass%, the content ratio of the surfactant in the composition is preferably 26 mass% or less, more preferably 24.5 mass% or less, further preferably 10 mass% or less, and further preferably 5 mass% or less.

[0107] When the content ratio of the surfactant in the composition is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.

[0108] [2.2.p-type semiconductor] The p-type semiconductor contained in the composition of the present embodiment may be a single type or a combination of two or more types.

[0109] The p-type semiconductor may be a low molecular compound or a high molecular compound, and is preferably a high molecular compound, and more preferably a π-conjugated high molecular compound.

[0110] Examples of polymer compound p-type semiconductors include: polyvinyl carbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure on the side chain or the main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyparaphenylene vinylene and its derivatives, polythiophene acetylene and its derivatives, polyfluorene and its derivatives.

[0111] (Donor-Acceptor Structure) The p-type semiconductor is preferably a polymer compound having a donor-acceptor structure. The donor-acceptor structure contains a donor structural unit and an acceptor structural unit. The donor structural unit is a structural unit with excess π electrons, and the acceptor structural unit is a structural unit lacking π electrons.

[0112] The structural units that can constitute the polymer compound having a donor-acceptor structure include structural units in which a donor structural unit and an acceptor structural unit are directly bonded, and further include structural units in which a donor structural unit and an acceptor structural unit are bonded via any appropriate spacer group (group or structural unit).

[0113] From the viewpoint of effectively reducing dark current, the p-type semiconductor is preferably a polymer compound containing one or more structural units selected from the group consisting of structural units represented by the following formula (I) and structural units represented by the following formula (II).

[0114] (Structural unit represented by formula (I))

[0115] [Chemistry 8]

[0116] In formula (I), Ar 1 and Ar 2 Each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents a group represented by any one of the following formulae (Z-1) to (Z-7).

[0117] [Chemistry 9]

[0118] In formulae (Z-1) to (Z-7), 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 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, an aryl group which may have a substituent, an alkoxy 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 imide residue which may have a substituent, an amide group which may have a substituent, an imide group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a cyano group, a nitro group, -C(=O)-R c The group represented by -SO2-R d The group represented by R c and R d Each independently represents a hydrogen 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 alkoxy group which may have a substituent, a cycloalkoxy group which may have a substituent, an aryloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. In formula (Z-1) to formula (Z-7), when there are two Rs, the two Rs may be the same or different. Z is preferably a group represented by formula (Z-4) or formula (Z-5).

[0119] R in formula (Z-1) to (Z-7) is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have a substituent. When there are multiple R groups, the multiple R groups may be the same or different from each other.

[0120] The structural unit represented by the formula (I) is preferably a structural unit represented by the following formula (I-1).

[0121] [Chemistry 10]

[0122] In formula (I-1), Z has the same meaning as described above.

[0123] Examples of the structural unit represented by the formula (I-1) include structural units represented by the following formulae (501) to (505).

[0124] [Chemistry 11]

[0125] In the above formulae (501) to (505), R has the same meaning as above. When there are two Rs, the two Rs may be the same or different.

[0126] The structural unit represented by formula (I) is preferably a group represented by the above formula (501).

[0127] (Structural unit represented by formula (II))

[0128] [Chemistry 12]

[0129] In the above formula (II), Ar 3 represents a divalent aromatic heterocyclic group. 3 The divalent aromatic heterocyclic group represented by is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20. 3 The divalent aromatic heterocyclic group represented by may have a substituent.

[0130] The structural unit represented by the formula (II) is preferably a structural unit represented by any one of the following formulae (II-1) to (II-8).

[0131] [Chemistry 13]

[0132] In formula (II-1) to formula (II-8), X 1 and X 2 Each independently represents a sulfur atom or an oxygen atom, and Z 1 and Z 2 Each independently represents a group represented by =C(R)- or a nitrogen atom, and R is as defined in formulae (Z-1) to (Z-7). A plurality of Rs may be the same as or different from each other.

[0133] In formula (II-6), it is preferred that two Rs are each independently a hydrogen atom, an alkyl group or a halogen atom, more preferably both are a hydrogen atom or a halogen atom, and even more preferably both are halogen atoms.

[0134] From the viewpoint of the availability of the raw material compound, X in Formula (II-1) to Formula (II-8) is preferably 1 and X 2 All of them are sulfur atoms.

[0135] As Ar 3 Examples of the divalent aromatic heterocyclic group represented by include groups represented by the following formulae (101) to (190). These groups may have a substituent.

[0136] [Chemistry 14]

[0137] [Chemistry 15]

[0138] [Chemistry 16]

[0139] [Chemistry 17]

[0140] In formulae (101) to (190), R has the same meaning as above. When there are plural Rs, the plural Rs may be the same as or different from each other.

[0141] In addition to the structural unit represented by the above formula (I) and / or the structural unit represented by the above formula (II), the p-type semiconductor may further have an arylene group. The arylene group refers to a divalent aromatic carbocyclic group. The arylene group may have a substituent.

[0142] The carbon number of the part after removing the substituent in the arylene group is usually 6 to 60, preferably 6 to 20. The carbon number of the arylene group including the substituent is usually 6 to 100.

[0143] Examples of the arylene group include a phenylene group, a naphthalene-diyl group, an anthracene-diyl group, a biphenyl-diyl group, a terphenyl-diyl group, a fluorene-diyl group, and a benzofluorene-diyl group.

[0144] When the p-type semiconductor is a polymer compound containing a structural unit represented by formula (I) and / or a structural unit represented by formula (II), the total amount of the structural unit represented by formula (I) and the structural unit represented by formula (II) is usually 20 to 100 mol%, preferably 40 to 100 mol%, and more preferably 50 to 100 mol%, based on the improvement of the charge transport property as a p-type semiconductor. Here, the amount of all structural units contained in the polymer compound is 100 mol%.

[0145] Preferred specific examples of the p-type semiconductor include the following polymer compounds.

[0146] [Chemistry 18]

[0147] (Content of p-type semiconductor) The content of the p-type semiconductor in the composition can be any appropriate content depending on the thickness of the required functional layer (active layer), desired characteristics, and the like. For example, based on 100 mass % of the composition, the p-type semiconductor content in the composition is preferably 0.1 mass % or more, more preferably 1 mass % or more, and is further preferably 20 mass % or less, more preferably 10 mass % or less.

[0148] [2.3.n-type semiconductor] The n-type semiconductor contained in the composition of the present embodiment may be a single type or a combination of two or more types.

[0149] The n-type semiconductor may be a low molecular compound or a high molecular compound. Examples of n-type semiconductors include: oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, dibenzoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, C 60 Fullerenes such as fullerene and fullerene derivatives as derivatives thereof (hereinafter sometimes referred to as fullerene compounds) and phenanthrene derivatives such as bathocuproine.

[0150] The n-type semiconductor can be C 60 Fullerenes such as fullerene and fullerene derivatives thereof may be non-fullerene compounds. In the following, fullerenes and fullerene derivatives may be referred to as fullerene compounds. Non-fullerene compounds refer to compounds other than fullerenes and fullerene derivatives.

[0151] (Fullerene compounds) In one embodiment, the n-type semiconductor contained in the composition is preferably at least one selected from fullerenes and fullerene derivatives, and more preferably a fullerene derivative.

[0152] Examples of fullerenes include: C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene and C 84 Fullerene. Examples of fullerene derivatives include derivatives of these fullerenes. Fullerene derivatives refer to compounds in which at least a part of fullerene is modified.

[0153] Examples of fullerene derivatives include compounds represented by the following formulas.

[0154] [Chemistry 19]

[0155] In the formula, R a represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a group having an ester structure, and these groups may have a substituent. a They may be the same as or different from each other. R brepresents an alkyl group, a cycloalkyl group or an aryl group, which may have a substituent. b They may be the same as or different from each other.

[0156] As R a Examples of the group having an ester structure represented by include groups represented by the following formulae.

[0157] [Chemistry 20]

[0158] In the formula, u1 represents an integer of 1 to 6. u2 represents an integer of 0 to 6. e represents an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.

[0159] As C 60 Examples of fullerene derivatives include the following compounds.

[0160] [Chemistry 21]

[0161] As C 70 Examples of fullerene derivatives include the following compounds.

[0162] [Chemistry 22]

[0163] Specific examples of fullerene derivatives include [6,6]-phenyl-C61-butyric acid methyl ester (C60PCBM, [6,6]-Phenyl C61 butyric acid methyl ester), [6,6]-phenyl-C71-butyric acid methyl ester (C70PCBM, [6,6]-Phenyl C71 butyric acid methyl ester), [6,6]-phenyl-C85-butyric acid methyl ester (C84PCBM, [6,6]-Phenyl C85 butyric acid methyl ester) and [6,6]-thienyl-C61-butyric acid methyl ester ([6,6]-Thienyl C61butyric acid methyl ester).

[0164] (Non-fullerene compounds) In other embodiments, the n-type semiconductor contained in the composition is preferably a non-fullerene compound. Various compounds are known as non-fullerene compounds, and any suitable non-fullerene compound known in the art can be used as the n-type semiconductor in this embodiment.

[0165] In one embodiment, the n-type semiconductor contained in the composition is preferably a compound containing a perylenetetracarboxylic acid diimide structure. Examples of the compound containing a perylenetetracarboxylic acid diimide structure that is not a fullerene compound include compounds represented by the following formula.

[0166] [Chemistry 23]

[0167] [Chemistry 24]

[0168] [Chemistry 25]

[0169] [Chemistry 26]

[0170] In the formula, R is as defined above. The multiple Rs may be the same as or different from each other.

[0171] In one embodiment, the n-type semiconductor is preferably a compound represented by the following formula (V). The compound represented by the following formula (V) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.

[0172] [Chemistry 27]

[0173] In the above formula (V), R 1 represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, a cycloalkoxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. 1 They may be the same as or different from each other.

[0174] Preferably, multiple R 1 Each is independently an alkyl group which may have a substituent.

[0175] R 2 represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, a cycloalkoxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. 2 They may be the same as or different from each other.

[0176] In another embodiment, the n-type semiconductor is preferably a compound represented by the following formula (VI). A 1 -B 10 -A 2(VI)

[0177] In formula (VI), A 1 and A 2 Each independently represents an electron-withdrawing group, B 10 It represents a group containing a π-conjugated system.

[0178] As A 1 and A 2 Examples of the electron withdrawing group include a group represented by -CH=C(-CN)2 and groups represented by the following formulae (a-1) to (a-9).

[0179] [Chemistry 28]

[0180] In formula (a-1) to formula (a-7), T represents a carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring may be a monocyclic ring or a condensed ring. When these rings have multiple substituents, the multiple substituents may be the same or different.

[0181] As examples of the carbocyclic ring that may have a substituent of T, an aromatic carbocyclic ring may be cited, preferably an aromatic carbocyclic ring. As specific examples of the carbocyclic ring that may have a substituent of T, a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring and a phenanthrene ring may be cited, preferably a benzene ring, a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and further preferably a benzene ring. These rings may have a substituent.

[0182] Examples of the heterocyclic ring that may have a substituent for T include aromatic heterocyclic rings, preferably aromatic heterocyclic rings. Specific examples of the heterocyclic ring that may have a substituent for T include pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring and thienothiophene ring, preferably thiophene ring, pyridine ring, pyrazine ring, thiazole ring and thienothiophene ring, more preferably thiophene ring. These rings may have a substituent.

[0183] Examples of the substituent that the carbocyclic ring or heterocyclic ring of T may have include a halogen atom, an alkyl group, an alkoxy group, an aryl group, and a monovalent heterocyclic group, and a fluorine atom and / or an alkyl group having 1 to 6 carbon atoms are preferred.

[0184] X 4 , X 5 and X 6 Each independently represents an oxygen atom, a sulfur atom, an alkylene group or a group represented by =C(-CN)2, and is preferably an oxygen atom, a sulfur atom or a group represented by =C(-CN)2.

[0185] X 7It represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group.

[0186] R a1 , R a2 , R a3 , R a4 and R a5 Each independently represents a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group, and is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.

[0187] [Chemistry 29]

[0188] In formula (a-8) and formula (a-9), R a6 and R a7 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 alkoxy group which may have a substituent, a cycloalkoxy group which may have a substituent, a monovalent aromatic carbocyclic group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. a6 and R a7 Can be the same or different.

[0189] As A 1 and A 2 The electron-withdrawing group is preferably a group represented by any one of the following formulas (a-1-1) to (a-1-4), (a-6-1) and (a-7-1), and more preferably a group represented by the following formula (a-1-1). a10 Each independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. a3 , R a4 and R a5 Each independently has the same meaning as defined above, and preferably each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

[0190] [Chemistry 30]

[0191] As B 10 Examples of the group containing a π-conjugated system include -(S 1 ) n1 -B 11 -(S 2 ) n2 - represents a group.

[0192] In this embodiment, the n-type semiconductor is preferably a compound represented by the following formula (VII). A 1 -(S 1 ) n1 -B 11 -(S 2 ) n2 -A 2 (VII)

[0193] In formula (VII), A 1 and A 2 Each independently represents an electron withdrawing group. 1 and A 2 Examples and preferred embodiments of A in the above formula (VI) 1 and A 2 The examples and preferred examples described are the same.

[0194] S 1 and S 2 Each independently represents a divalent carbocyclic group which may have a substituent, a divalent heterocyclic group which may have a substituent, -C(R s1 )=C(R s2 )-represented group (wherein, R s1 and R s2 Each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent). ) or a group represented by -C≡C-.

[0195] S 1 and S 2 The divalent carbocyclic group or divalent heterocyclic group which may have a substituent represented by may be a condensed ring. When the divalent carbocyclic group or divalent heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

[0196] In formula (VII), n1 and n2 each independently represent an integer of 0 or more, preferably each independently represent 0 or 1, and more preferably represent 0 and 1 simultaneously.

[0197] Examples of the divalent carbocyclic group include divalent aromatic carbocyclic groups. Examples of the divalent heterocyclic group include divalent aromatic heterocyclic groups. When the divalent aromatic carbocyclic group or divalent aromatic heterocyclic group is a condensed ring, all of the rings constituting the condensed ring may be aromatic condensed rings, or only a part of them may be aromatic condensed rings.

[0198] As S 1 and S 2Examples include: 3 Examples of the divalent aromatic heterocyclic group represented by the formulae include groups represented by any one of the formulae (101) to (190), and groups in which a hydrogen atom in these groups is substituted by a substituent.

[0199] Preferred S 1 and S 2 Each independently represents a group represented by the following formula (s-1) or (s-2).

[0200] [Chemistry 31]

[0201] In formula (s-1) and (s-2), X 3 represents an oxygen atom or a sulfur atom. R a10 As defined above.

[0202] Preferred S 1 and S 2 Each independently represents a group represented by formula (142), formula (148) or formula (184), or a group in which a hydrogen atom in these groups is substituted by a substituent, and more preferably a group represented by the above formula (142) or formula (184), or a group in which one hydrogen atom in the group represented by formula (184) is substituted by an alkoxy group.

[0203] B 11 It represents a fused ring group of two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and is a fused ring group which does not contain an ortho-peri fused structure and may have a substituent.

[0204] B 11 The fused ring group represented may include a structure in which two or more identical structures are fused together.

[0205] B 11 When the fused ring group represented by has a plurality of substituents, the plurality of substituents may be the same as or different from each other.

[0206] As a component B 11 Examples of the carbocyclic structure of the fused ring group represented by include the ring structure represented by the following formula (Cy1) or formula (Cy2).

[0207] [Chemistry 32]

[0208] As a component B 11 Examples of the heterocyclic structure of the fused ring group represented by include any one of the ring structures represented by the following formula (Cy3) to formula (Cy10).

[0209] [Chemistry 33]

[0210] In formula (VII), B 11 It is preferably a fused ring group of two or more structures selected from the group consisting of the structures represented by the above formula (Cy1) to formula (Cy10), does not contain an ortho-peri fused structure, and may have a substituent. 11 A structure in which two or more identical structures among the structures represented by formula (Cy1) to formula (Cy10) are fused together may also be included.

[0211] B 11 More preferably, it is a fused ring group of two or more structures selected from the group consisting of structures represented by formula (Cy1) to formula (Cy6) and formula (Cy8), does not contain an ortho-peri fused structure, and may have a substituent.

[0212] B 11 The substituent that the fused ring group may have is preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, and a monovalent heterocyclic group that may have a substituent. 11 The aryl group which the fused ring group represented may have may be substituted with, for example, an alkyl group.

[0213] As B 11 Examples of fused ring groups include groups represented by the following formulae (b-1) to (b-14) and groups in which hydrogen atoms in these groups are substituted by substituents (preferably alkyl groups which may have substituents, aryl groups which may have substituents, alkoxy groups which may have substituents, or monovalent heterocyclic groups which may have substituents).

[0214] As B 11 The fused ring group is preferably a group represented by the following formula (b-2) or (b-3) or a group in which the hydrogen atoms in these groups are substituted by a substituent (preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent), and is more preferably a group represented by the following formula (b-2) or (b-3).

[0215] [Chemistry 34]

[0216] [Chemistry 35]

[0217] In formula (b-1) to formula (b-14), R a10 As defined above. In formula (b-1) to formula (b-14), the plurality of Ra10 Each independently is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.

[0218] Examples of the compound represented by formula (VI) or formula (VII) include compounds represented by the following formulae.

[0219] [Chemistry 36]

[0220] [Chemistry 37]

[0221] In the above formula, R is as defined above, and X represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. In the above formula, R is preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent.

[0222] The composition may contain only a non-fullerene compound or only a fullerene compound as an n-type semiconductor, or may contain a non-fullerene compound and a fullerene compound in combination.

[0223] Preferred specific examples of the n-type semiconductor contained in the composition include compounds represented by the following formula:

[0224] [Chemistry 38]

[0225] (Content of n-type semiconductor) The content of the n-type semiconductor in the composition can be any appropriate content depending on the thickness of the required functional layer (active layer), desired characteristics, and the like. For example, based on 100 mass % of the composition, the content of the n-type semiconductor in the composition is preferably 0.1 mass % or more, more preferably 1 mass % or more, and is further preferably 20 mass % or less, more preferably 10 mass % or less.

[0226] (Mass ratio of p-type semiconductor to n-type semiconductor (p-type semiconductor / n-type semiconductor)) The mass ratio of the p-type semiconductor to the n-type semiconductor in the composition (p-type semiconductor / n-type semiconductor) is preferably 1 / 9 or more, more preferably 1 / 5 or more, further preferably 1 / 3 or more, further preferably 9 / 1 or less, more preferably 5 / 1 or less, further preferably 3 / 1 or less. When the composition contains multiple p-type semiconductors, the mass ratio is the total mass ratio of the p-type semiconductors; when the composition contains multiple n-type semiconductors, the mass ratio is the total mass ratio of the n-type semiconductors.

[0227] [2.4.Solvent] The solvent contained in the composition of the present embodiment may be a single type or a combination of two or more types.

[0228] The composition of this embodiment may further contain an aromatic hydrocarbon as a solvent, preferably an aromatic hydrocarbon. The aromatic hydrocarbon may have a substituent. As the aromatic hydrocarbon, a compound capable of dissolving the p-type semiconductor described above is particularly preferred.

[0229] Examples of aromatic hydrocarbons that can be used as a solvent include toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), trimethylbenzenes (e.g., mesitylene, 1,2,4-trimethylbenzene (trimethylol)), butylbenzenes (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1,2,3,4-tetrahydronaphthalene (tetralin), indane, 1-chloronaphthalene, chlorobenzene, and dichlorobenzene (1,2-dichlorobenzene).

[0230] The solvent may be composed of only one kind of aromatic hydrocarbon or may be composed of two or more kinds of aromatic hydrocarbons.

[0231] The aromatic hydrocarbon that can constitute the solvent is preferably one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene).

[0232] The content of the aromatic hydrocarbon solvent in the solvent is preferably 80% by mass or more, more preferably 90% by mass or more, and usually 100% by mass or less, based on 100% by mass of the total mass of the solvent.

[0233] The composition of the present embodiment may further contain an alkyl halide as a solvent. Examples of the alkyl halide that can be used as a solvent include chloroform.

[0234] In the composition of the present embodiment, in addition to the above-mentioned solvent, a further selected solvent may be used in combination from the viewpoint of improving the solubility of the n-type semiconductor.

[0235] In the present embodiment, further examples of the solvent include: aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds. The composition of the present embodiment may contain, as a solvent, one or more compounds selected from the group consisting of aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds.

[0236] Examples of the aromatic carbonyl compound include acetophenone, propiophenone, butylphenone, cyclohexylphenylketone, and benzophenone. These compounds may have a substituent.

[0237] Examples of the aromatic ester compound include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopropyl benzoate, benzyl benzoate, cyclohexyl benzoate, and phenyl benzoate. These compounds may have a substituent.

[0238] Examples of the nitrogen-containing heterocyclic compound include pyridine, quinoline, quinoxaline, 1,2,3,4-tetrahydroquinoline, pyrimidine, pyrazine, and quinazoline. These nitrogen-containing heterocyclic compounds may have a substituent.

[0239] The nitrogen-containing heterocyclic compound may have a substituent directly bonded to the ring structure. Examples of the substituent that the ring structure of the nitrogen-containing heterocyclic compound may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and an alkylthio group.

[0240] Taking the total mass of the composition as 100 mass%, from the viewpoint of further improving the solubility of p-type semiconductors and n-type semiconductors, the total mass of the solvent contained in the composition of this embodiment is preferably 90 mass% or more, more preferably 92 mass% or more, and further preferably 95 mass% or more. From the viewpoint of further increasing the concentration of p-type semiconductors and n-type semiconductors in the composition and facilitating the formation of a layer with a certain thickness or more, it is preferably 99.9 mass% or less.

[0241] [2.5. Optional ingredients] In addition to the above-mentioned p-type semiconductor, n-type semiconductor, surfactant and solvent, the composition of this embodiment may further contain any component within the limit that does not impair the purpose and effect of the present invention. Examples of the optional component include: ultraviolet absorbers, antioxidants, sensitizers for sensitizing the function of generating charges by absorbing light, and light stabilizers for increasing the stability against ultraviolet rays.

[0242] The total content of the optional components in the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and is usually 0% by mass or more, and may be 0% by mass.

[0243] [2.6. Properties of the composition, etc.] The p-type semiconductor and the n-type semiconductor may be dissolved in the composition or may be dispersed in the composition. Preferably, at least a part of the p-type semiconductor and the n-type semiconductor is dissolved in the composition.

[0244] For the total concentration of the p-type semiconductor and the n-type semiconductor in the composition of the present embodiment, it can be set to any appropriate concentration according to the thickness of the desired functional layer (active layer), the desired characteristics, etc. The total concentration of the p-type semiconductor and the n-type semiconductor is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 0.01% by mass or more and 20% by mass or less, further preferably 0.01% by mass or more and 10% by mass or less, further preferably 0.01% by mass or more and 5% by mass or less, and particularly preferably 0.1% by mass or more and 5% by mass or less.

[0245] [2.7. Method for producing composition] The composition can be produced by a conventionally known method. The solvent, the p-type semiconductor, the n-type semiconductor, and the surfactant can be mixed by heating to a temperature below the boiling point of the solvent.

[0246] The solvent, the p-type semiconductor, the n-type semiconductor and the surfactant are mixed, and the resulting mixture is filtered through a filter, and the resulting filtrate is used as the composition. As the filter, for example, a filter made of a fluorine-containing resin such as polytetrafluoroethylene (PTFE) can be used.

[0247] [2.8. Use of the composition] The composition can be preferably used as ink for use in forming a film containing a p-type semiconductor, an n-type semiconductor, and a surfactant by a coating method.

[0248] In this specification, "ink" refers to a liquid substance used in a coating method, and is not limited to a colored liquid. In addition, "coating method" includes a method of forming a film (layer) using a liquid substance. Examples of coating methods include: slit die coating, slit coating, blade coating, casting, micro-gravure coating, gravure coating, rod coating, roller coating, wire rod coating, dip coating, spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, applicator printing, nozzle coating, and capillary coating.

[0249] [3. Membrane] A film according to one embodiment of the present invention contains a p-type semiconductor, an n-type semiconductor, and a surfactant. The film can be preferably used as an active layer included in a photoelectric conversion element.

[0250] Examples and preferred examples of the p-type semiconductor, n-type semiconductor and surfactant contained in the film are the same as the examples and preferred examples of the p-type semiconductor, n-type semiconductor and surfactant that may be contained in the above-mentioned composition, respectively.

[0251] The content of the p-type semiconductor in the film of this embodiment can be set to any appropriate content depending on desired characteristics and the like. For example, the p-type semiconductor content in the film is preferably 1 mass % or more, more preferably 10 mass % or more, further preferably 20 mass % or more, and also preferably 99 mass % or less, more preferably 90 mass % or less, further preferably 80 mass % or less.

[0252] The content of the n-type semiconductor in the film of this embodiment can be set to any appropriate content depending on desired characteristics and the like. For example, the n-type semiconductor content in the film is preferably 1 mass % or more, more preferably 10 mass % or more, further preferably 20 mass % or more, and further preferably 99 mass % or less, more preferably 90 mass % or less, further preferably 80 mass % or less.

[0253] The mass ratio of the p-type semiconductor to the n-type semiconductor (p-type semiconductor / n-type semiconductor) in the film of this embodiment is usually the same as the mass ratio of the p-type semiconductor to the n-type semiconductor in the composition for producing the film.

[0254] Taking the total mass of the n-type semiconductor, the p-type semiconductor and the surfactant as 100 mass %, the content ratio of the surfactant in the film of this embodiment is preferably 0.1 mass % or more, more preferably 1 mass % or more, and further preferably 10 mass % or less, more preferably 5 mass % or less.

[0255] It is preferred that the film of the present embodiment contains substantially no solvent. The solvent content in the film of the present embodiment is preferably 1% by mass or less, more preferably 0.1% by mass or less, and is usually 0% by mass or more, and may be 0% by mass.

[0256] The film of the present embodiment can be produced by any method. For example, the film of the present embodiment can be produced by a production method including the step (i) of applying the composition to a coating object to obtain a coating film and the step (ii) of removing the solvent from the obtained coating film.

[0257] (Process (i)) In step (i), as a method for applying the composition to the coating object, any conventionally known coating method as described above can be used.

[0258] In step (i), the composition is applied to any coating target. In the process of manufacturing a photoelectric conversion element, the composition can be applied to a functional layer that can be included in the photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer or a hole transport layer.

[0259] (Step (ii)) In step (ii), any appropriate method may be used as a method for removing the solvent from the coating film of the composition formed in step (i). Examples of the method for removing the solvent include hot air drying, infrared heating drying, flash lamp annealing drying, reduced pressure drying and the like.

[0260] [4. Organic photoelectric conversion element] [4.1. Configuration of Photoelectric Conversion Element] The photoelectric conversion element according to this embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode. The active layer is the film described above. Hereinafter, a configuration example of the photoelectric conversion element according to the present embodiment will be described in detail with reference to the drawings.

[0261] Figure 1 This is a diagram schematically showing a configuration example of a photoelectric conversion element.

[0262] like Figure 1 As shown, the photoelectric conversion element 10 is provided on a supporting substrate 11. The photoelectric conversion element 10 includes a first electrode 12 provided in contact with the supporting substrate 11, a first intermediate layer 13 provided in contact with the first electrode 12, an active layer 14 provided in contact with the first intermediate layer 13, a second intermediate layer 15 provided in contact with the active layer 14, and a second electrode 16 provided in contact with the second intermediate layer 15. In this configuration example, a packaging component 17 is further provided in contact with the second electrode 16. In this embodiment, the first intermediate layer 13 and the second intermediate layer 15 are provided, but only one of the first intermediate layer 13 and the second intermediate layer 15 may be provided. For example, the first intermediate layer 13 may not be provided. For example, the second intermediate layer 15 may not be provided.

[0263] The constituent elements that may be included in the photoelectric conversion element of this embodiment will be described in detail below.

[0264] (Substrate) The photoelectric conversion element is usually formed on a substrate (support substrate). In addition, there is a case where it is further packaged by a substrate (package substrate). One of a pair of electrodes consisting of a first electrode and a second electrode is usually formed on the substrate. There is no particular limitation on the material of the substrate as long as it is a material that does not undergo chemical property changes when forming a layer containing an organic compound.

[0265] As the material of the substrate, for example, glass, plastic, polymer film, silicon can be cited. When an opaque substrate is used, it is preferred that the electrode in the opposite direction to the electrode disposed on one side of the opaque substrate (in other words, the electrode away from the side of the opaque substrate) is set to a transparent or semi-transparent electrode.

[0266] (electrode) The photoelectric conversion element includes a first electrode and a second electrode as a pair of electrodes. At least one of the first electrode and the second electrode is preferably a transparent or semi-transparent electrode in order to allow light to enter.

[0267] Examples of transparent or translucent electrode materials include: conductive metal oxide films, translucent metal films. Specifically, examples include: indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), NESA, etc., as composites thereof, gold, platinum, silver, and copper. As transparent or translucent electrode materials, ITO, IZO, and tin oxide are preferred. In addition, as electrodes, transparent conductive films made of organic compounds such as polyaniline and its derivatives, polythiophene and its derivatives can also be used. The transparent or translucent electrode can be the first electrode or the second electrode.

[0268] If one of the electrodes in a pair of electrodes is transparent or translucent, the other electrode may also be an electrode with low light transmittance. Examples of electrode materials with low light transmittance include metals and conductive polymers. Specific examples of electrode materials with low light transmittance 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, and alloys of two or more of these, or alloys of one or more of these metals and one or more of the metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, petroleum graphite, petroleum graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. As alloys, magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

[0269] (Active layer) The photoelectric conversion element of this embodiment includes the above-described film as an active layer. The active layer of this embodiment has a bulk heterojunction structure.

[0270] In this embodiment, the thickness of the active layer is not particularly limited. For the thickness of the active layer, for example, the balance between suppressing the dark current and taking out the generated photocurrent can be considered and set to any appropriate thickness. In particular, from the viewpoint of further reducing the dark current, the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and further preferably 200 nm or more. In addition, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 1 μm or less.

[0271] (Middle layer) like Figure 1As shown, the photoelectric conversion element of this embodiment preferably includes an intermediate layer (buffer layer) such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer) as a component for improving characteristics such as photoelectric conversion efficiency.

[0272] Examples of the material for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and a mixture of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonic acid)) (PEDOT:PSS).

[0273] The intermediate layer can be formed by any conventionally known appropriate formation method, and can also be formed by a vacuum deposition method or a coating method similar to the formation method of the active layer.

[0274] like Figure 1 As shown, the photoelectric conversion element of this embodiment preferably includes an electron transport layer as a first intermediate layer between the first electrode and the active layer. The photoelectric conversion element of this embodiment may or may not include a hole transport layer as a second intermediate layer between the second electrode and the active layer.

[0275] In another embodiment, the photoelectric conversion element preferably includes an electron transport layer as a second intermediate layer between the second electrode and the active layer. In this other embodiment, the photoelectric conversion element may or may not include a hole transport layer as a first intermediate layer between the first electrode and the active layer.

[0276] The electron transport layer has the function of transporting electrons from the active layer to the electrode, and the hole transport layer has the function of transporting holes from the active layer to the electrode.

[0277] In particular, there is a case where the electron transport layer provided in contact with the electrode is called the electron injection layer. The electron transport layer (electron injection layer) provided in contact with the electrode has the function of promoting the injection of electrons into the electrode. The electron transport layer (electron injection layer) may be in contact with the active layer.

[0278] The electron transport layer contains an electron transport material. Examples of the electron transport material include polyalkylene imine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

[0279] Examples of polyalkyleneimines and their derivatives include alkyleneimines having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, and polymers obtained by polymerizing one or more alkyleneimines having 2 to 4 carbon atoms by conventional methods, and polymers chemically modified by reacting these with various compounds. Polyalkyleneimines and their derivatives are preferably polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

[0280] Examples of the polymer compound containing a fluorene structure include poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-o-2,7-(9,9′-dioctylfluorene)] (PFN) and PFN-P2.

[0281] Examples of the metal oxide include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. The metal oxide is preferably a metal oxide containing zinc, and zinc oxide is particularly preferred.

[0282] Examples of other electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0283] In particular, a hole transport layer provided in contact with an electrode may be referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with an electrode has a function of promoting injection of holes generated in the active layer into the electrode.

[0284] 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, tungsten oxide (WO3) and molybdenum oxide (MoO3).

[0285] (Packaging components) The photoelectric conversion element of the present embodiment preferably further includes a sealing member, and is sealed into a package body by the sealing member. Any suitable conventionally known sealing member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.

[0286] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0287] The encapsulation layer is preferably formed of a material having a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of materials suitable for the encapsulation layer include organic materials such as polytrifluoroethylene, polychlorotrifluoroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

[0288] The packaging member is generally made of a material that can withstand a heat treatment performed when the photoelectric conversion element is incorporated into a device, for example, an applicable example described later.

[0289] In other embodiments, the first intermediate layer 13 and the second intermediate layer 15 or either one of them may not be provided.

[0290] [4.2. Method for manufacturing photoelectric conversion element] The photoelectric conversion element of this embodiment can be produced by any conventionally known appropriate production method. The photoelectric conversion element of this embodiment can be produced by a process of combining materials appropriately selected when forming components.

[0291] Hereinafter, as an embodiment of the present invention, a method for manufacturing a photoelectric conversion element having a structure in which a substrate (support substrate), a first electrode, a hole transport layer, an active layer, an electron transport layer, and a second electrode are in contact with each other in this order will be described.

[0292] (Step of preparing substrate) In this process, for example, a supporting substrate provided with a first electrode is prepared. Alternatively, a substrate provided with a conductive film formed using the electrode material described above can be purchased from the market, and a conductive film pattern is formed as needed to form the first electrode to prepare the supporting substrate provided with the first electrode.

[0293] In the manufacturing method of the photoelectric conversion element involved in this embodiment, the method for forming the first electrode when forming the first electrode on the supporting substrate is not particularly limited. For the first electrode, the material described above can be formed on the structure (such as the supporting substrate, the active layer, the hole transport layer) by any suitable method known in the art, such as vacuum evaporation, sputtering, ion plating, electroplating, and coating.

[0294] (Hole Transport Layer Formation Step) The method for producing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.

[0295] The method for forming the hole transport layer is not particularly limited. From the perspective of simplifying the process for forming the hole transport layer, the hole transport layer is preferably formed 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 solution containing the material and solvent that can constitute the hole transport layer as described above, or by a vacuum evaporation method.

[0296] (Active Layer Formation Step) In the method for manufacturing a photoelectric conversion element of this embodiment, an active layer is formed on the hole transport layer. The active layer can be formed by any suitable conventionally known formation process. In this embodiment, the active layer can be manufactured by a coating method using the composition described above.

[0297] The active layer can be formed in the same manner as the "film" described above. In this embodiment, the active layer can be formed by a process including applying a composition containing a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent on the hole transport layer to form a coating film and drying the coating film.

[0298] (Step of Forming Electron Transport Layer) The method for manufacturing a photoelectric conversion element of the present embodiment may include a step of forming an electron transport layer (electron injection layer) provided so as to be in contact with the active layer.

[0299] The method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the electron transport layer, the electron transport layer is preferably formed by any suitable vacuum deposition method known in the art.

[0300] (Second Electrode Formation Step) The method for forming the second electrode is not particularly limited. The second electrode can be formed by any suitable method known in the art, such as coating, vacuum evaporation, sputtering, ion plating, electroplating, etc., on the electrode material exemplified above. The photoelectric conversion element of this embodiment can be manufactured by the above steps.

[0301] (Package Forming Step) When forming a package, in this embodiment, any suitable packaging material (adhesive) and substrate (package substrate) known in the art are used. Specifically, a sealing material such as a UV curable resin is coated on a supporting substrate in a manner surrounding the periphery of the manufactured photoelectric conversion element, and after seamless bonding using the sealing material, the photoelectric conversion element is packaged in the gap between the supporting substrate and the package substrate by irradiating the selected sealing material with suitable UV light, thereby obtaining a package of the photoelectric conversion element.

[0302] [4.3. Application examples of photoelectric conversion elements] The photoelectric conversion element of this embodiment can be used for, for example, a light detection element and a solar cell. The photoelectric conversion element of this embodiment can generate photovoltaic power between electrodes by light irradiation and operate as a solar cell. A solar cell module can also be made by integrating a plurality of photoelectric conversion elements.

[0303] The photoelectric conversion element of this embodiment can be operated as a light detection element (light sensor) by irradiating light from one side of a transparent or semi-transparent electrode under a state of an applied voltage (reverse bias) between the electrodes, thereby flowing a photocurrent. In addition, it can also be used as an image sensor by integrating multiple light detection elements. In particular, the photoelectric conversion element of this embodiment can be preferably used as a light detection element.

[0304] The photoelectric conversion element according to this embodiment can be preferably used as a light detection element in detection units provided in various electronic devices such as workstations, personal computers, mobile information terminals, access control systems, digital cameras, and medical instruments.

[0305] The photoelectric conversion element of this embodiment can be preferably applied to image detection units for solid-state imaging devices such as X-ray imaging devices and CMOS image sensors equipped in the above-mentioned exemplified electronic devices (for example, image sensors such as X-ray sensors), detection units (for example, near-infrared sensors) of biometric information authentication devices that detect partial specified features 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.

[0306] The photoelectric conversion element of the present embodiment can also be preferably applied to a time-of-flight distance measuring device (TOF distance measuring device) as an image detection unit for a solid-state imaging device.

[0307] In a TOF type distance measuring device, the distance is measured by using a photoelectric conversion element to receive the reflected light reflected by the radiated light from the light source in the measured object. Specifically, the flight time of the irradiated light emitted by the light source reflected by the measured object and returned as reflected light is detected to find the distance to the measured object. In the TOF type, there are direct TOF methods and indirect TOF methods. In the direct TOF method, the difference between the moment when the light is irradiated by the light source and the moment when the reflected light is received by the photoelectric conversion element is directly calculated. In the indirect TOF method, the change in the charge storage amount that depends on the flight time is converted into a time change, thereby calculating the distance. In the distance measurement principle of measuring the flight time by charge storage used in the indirect TOF method, there are continuous wave (especially sine wave) modulation methods and pulse modulation methods that calculate the flight time by the phase of the irradiated light emitted by the light source and the reflected light reflected by the measured object. The photoelectric conversion element of this embodiment can be applied to any measuring device of these methods.

[0308] [5. Light detection element] As described above, the photoelectric conversion element of this embodiment has a light detection function that can convert the emitted light into an electrical signal according to the amount of light received, and output it to an external circuit via an electrode. Therefore, the photoelectric conversion element involved in the embodiment of the present invention can be particularly preferably used as a light detection element with a light detection function. Among them, the light detection element of this embodiment can be the photoelectric conversion element itself, and can also contain a functional element for controlling voltage, etc. in addition to the photoelectric conversion element. Example

[0309] Hereinafter, examples are shown to further illustrate the present invention in detail. The present invention is not limited to the following examples. In the following examples, unless otherwise specified, the conditions of normal temperature (20°C ± 15°C) and normal pressure (1 atm) are used. In addition, "%" and "parts" each represent "mass %" and "mass parts" unless otherwise specified.

[0310] <Semiconductor materials used> (p-type semiconductor) As the p-type semiconductor material P-1, a polymer compound synthesized by the method described in Reference International Publication No. 2013 / 051676 was used. As the p-type semiconductor material P-2, a polymer compound synthesized by the method described in Reference International Publication No. 2011 / 052709 was used. As the p-type semiconductor material P-3, a polymer compound, trade name PM6 manufactured by 1-material, was used. As the p-type semiconductor material P-4, a polymer compound, trade name: PCE10 manufactured by 1-material, was used.

[0311] (n-type semiconductor) As the n-type semiconductor material N-1, Guard Surf NC-1010 manufactured by Harves Corporation was used. As the n-type semiconductor material N-2, trade name: E100 manufactured by Frontier Carbon Corporation was used. As the n-type semiconductor material N-3, trade name: Y6 manufactured by 1-material was used.

[0312] The specific structures of the p-type semiconductor materials P-1 to P-4 and the n-type semiconductor materials N-1 to N-3 are shown in Tables 1 and 2 below.

[0313] [Table 1]

[0314] [Table 2]

[0315] <Surfactant used> The surfactants used in the examples are as follows. “F-556”: a nonionic fluorinated surfactant having a poly(meth)acrylate structure manufactured by DIC Corporation. “R-40”: a nonionic fluorinated surfactant having a poly(meth)acrylate structure manufactured by DIC Corporation. "KP-620": A nonionic surfactant having an organopolysiloxane structure manufactured by Shin-Etsu Chemical Co., Ltd. "KP-323": A nonionic surfactant having an organopolysiloxane structure manufactured by Shin-Etsu Chemical Co., Ltd.

[0316] The physical properties of the above surfactants are shown in the following table. In the following table, "F" represents a fluorine atom.

[0317] [Table 3]

[0318] The viscosity η of the surfactant can be measured by the following method and conditions. The Modular Compact Rheometer MCR302 manufactured by Anton Paar was used to measure the flow rate at 25°C and a shear rate of 100 (S -1 ) under viscosity η.

[0319] The Mp (peak molecular weight) of the surfactant can be measured by the following method and conditions. As the mobile phase of GPC, o-dichlorobenzene was used at a flow rate of 1.0 mL / min. As the chromatographic column, Shodex KD-806M manufactured by Showa Denko K.K. was used, and as the guard column, Shodex KD-G manufactured by Showa Denko K.K. was used.

[0320] As detectors, a UV-vis detector (SPD-M20A manufactured by Shimadzu Corporation) and a differential refractive index detector (RID-10A manufactured by Shimadzu Corporation) were used.

[0321] The compound to be measured (polymer) and 1-chloronaphthalene as a solvent were mixed to a concentration of 0.05% by mass, and the mixture was stirred at 80° C. for 2 hours to dissolve the mixture to prepare a solution.

[0322] 10 μL of the obtained solution was injected as a sample into the above-mentioned measuring device (GPC), and the peak molecular weight (Mp) was measured.

[0323] <Example 1> The ink solvent was prepared by mixing trimethylolbenzene, tetralin and butyl benzoate in a mass ratio of 87%, 10% and 3%, respectively. As a surfactant, "F-556" manufactured by DIC Corporation was used. The ink solvent and the surfactant were mixed in a mass ratio of 99.9%:0.1% to prepare a mixture (a). A mixture (b) is prepared by mixing a material P-1 as a p-type semiconductor and a material N-1 as an n-type semiconductor with a mixture (a). The mixing amount of the p-type semiconductor is 1.5% by mass relative to the entire ink composition (mixture (b)). The mixing amount of the n-type semiconductor is 1.5% by mass relative to the entire ink composition (mixture (b)). The obtained mixture (b) is stirred at 60°C for 6 hours and then filtered using a filter to prepare an ink composition I-1. When the total of the solvent, p-type semiconductor, n-type semiconductor and surfactant contained in the ink composition I-1 is 100% by mass, the content ratio of the surfactant is 0.097% by mass.

[0324] <Example 2> The ink solvent and the surfactant were mixed in a mass ratio of 99.9%:0.1% to prepare a mixture (a). Ink composition I-2 was prepared in the same manner as in Example 1 except for the above matters. When the total of the solvent, p-type semiconductor, n-type semiconductor and surfactant contained in ink composition I-2 was taken as 100 mass %, the content ratio of the surfactant was 0.97 mass %.

[0325] <Example 3> As a surfactant, "KP-620" manufactured by Shin-Etsu Chemical Co., Ltd. was used. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-3.

[0326] <Comparative Example 1> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-C1.

[0327] <Example 4> Trimethylolbenzene and 1,2-dimethoxybenzene were mixed at a mass ratio of 97% and 3%, respectively, to prepare an ink solvent. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-4.

[0328] <Comparative Example 2> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 4 was carried out to prepare ink composition I-C2.

[0329] <Example 5> Material P-2 is used as a p-type semiconductor; material N-2 is used as an n-type semiconductor. As a surfactant, "R-40" manufactured by DIC Corporation was used. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-5.

[0330] <Example 6> Material P-2 is used as a p-type semiconductor; material N-2 is used as an n-type semiconductor. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-6.

[0331] <Comparative Example 3> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 5 was carried out to prepare ink composition I-C3.

[0332] <Example 7> Material P-3 was used as a p-type semiconductor, material N-2 was used as an n-type semiconductor, and o-dichlorobenzene was used as an ink solvent. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-7.

[0333] <Comparative Example 4> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 7 was carried out to prepare ink composition I-C4.

[0334] <Example 8> Material P-4 was used as a p-type semiconductor, material N-2 was used as an n-type semiconductor, and o-dichlorobenzene was used as an ink solvent. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-8.

[0335] <Comparative Example 5> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 8 was carried out to prepare ink composition I-C5.

[0336] <Example 9> Material P-1 is used as a p-type semiconductor; material N-2 is used as an n-type semiconductor. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-9.

[0337] <Comparative Example 6> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 9 was carried out to prepare ink composition I-C6.

[0338] <Example 10> Material P-1 is used as a p-type semiconductor; material N-3 is used as an n-type semiconductor. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-10.

[0339] <Comparative Example 7> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 10 was carried out to prepare ink composition I-C7.

[0340] <Example 11> Material P-3 is used as a p-type semiconductor; material N-3 is used as an n-type semiconductor. Except for the above matters, the same operation as in Example 1 was carried out to prepare ink composition I-11.

[0341] <Comparative Example 8> Instead of mixture (a), an ink solvent containing no surfactant is used. Except for the above matters, the same operation as in Example 11 was carried out to prepare ink composition I-C8.

[0342] The mixing of the ink compositions according to the examples and comparative examples is shown in the following table. In the following table, the amount of surfactant added is shown as a value based on 100% by mass of the mixture (b).

[0343] [Table 4]

[0344] <Manufacturing and Evaluation of Photoelectric Conversion Elements> Using each ink composition produced in Examples and Comparative Examples, a photoelectric conversion element was produced according to the following photoelectric conversion element production method A or production method B, and the dark current (Jd) was measured.

[0345] [Photoelectric conversion element manufacturing method A] (A-1. Preparation of substrate) A glass substrate (hereinafter referred to as a glass substrate) on which a 100 nm thick ITO film as a first electrode was formed by sputtering was prepared. Next, the glass substrate was subjected to a surface treatment by ozone ultraviolet (UV) treatment.

[0346] (A-2. Formation of Active Layer) The ink composition was applied to the ITO film of the glass substrate by spin coating to form a coating. The glass substrate with the coating was placed on a hot plate, and the coating was dried in the atmosphere at 70°C for 2 minutes. Next, the glass substrate with the coating was placed on a hot plate, and the coating was further dried in a nitrogen atmosphere at 100°C for 10 minutes. Thus, an active layer was formed on the ITO film. The thickness of the formed active layer was about 250nm.

[0347] (A-3. Formation of Electron Transport Layer) Next, a 45% by mass isopropanol dispersion of zinc oxide nanoparticles (particle size 20-30 nm) (manufactured by Tayca, HTD-711Z) was diluted with 10 times the mass of 3-pentanol to prepare a coating solution. The coating solution was applied to the active layer formed by spin coating at a thickness of 40 nm and heated at 70° C. for 5 minutes. Thus, an electron transport layer was formed on the active layer.

[0348] (A-4. Forming electrodes) Thereafter, a Ag film as an electrode (second electrode) was formed on the electron transport layer to a thickness of about 80 nm using a resistance heating vapor deposition apparatus.

[0349] (A-5. Formation of Encapsulation Layer) Next, an ultraviolet (UV) curable sealant was applied around the glass substrate on which the electrode (second electrode) was formed, and after the glass plate was further bonded to the top of the electrode, the sealant was cured and sealed by irradiation with UV light to obtain a photoelectric conversion element. The obtained photoelectric conversion element had a square shape of 2 mm×2 mm.

[0350] By the above-described manufacturing method, a photoelectric conversion element A (light detection element A) in which a glass substrate, a first electrode, an active layer, an electron transport layer, and a second electrode are provided in this order can be manufactured.

[0351] [Photoelectric conversion element manufacturing method B] (B-1. Preparation of substrate) A glass substrate on which a 100 nm thick ITO film was formed by sputtering was prepared. Next, the glass substrate was subjected to a surface treatment by ozone UV treatment.

[0352] (B-2. Formation of Electron Transport Layer) Next, the glass substrate was immersed in a diluted solution of 80% ethoxylated polyethyleneimine aqueous solution (manufactured by Sigma-Aldrich, 37% by mass aqueous solution) diluted with water to a concentration of 0.1% by mass for 5 minutes. Next, the glass substrate was taken out of the diluted solution and placed on a hot plate, and dried in the atmosphere at 100° C. for 10 minutes.

[0353] Next, the dried glass substrate was washed with water, placed on a hot plate, and dried in air at 100° C. for 10 minutes. Thus, an electron transport layer was formed on the ITO film serving as the first electrode.

[0354] (B-3. Formation of Active Layer) Next, the ink composition was applied to the electron transport layer formed on the ITO film by a slit die coating method to form a coating. Next, a vacuum drying treatment was performed for 5 minutes (pressure 10 Pa, 70°C). The glass substrate with the coating after the drying treatment was placed on a hot plate and dried at 100°C for 12 minutes to form an active layer. The thickness of the formed active layer was about 530nm.

[0355] (B-4. Forming electrodes) Next, a suspension obtained by dissolving poly(3,4-ethylenedioxythiophene) / polystyrene sulfonic acid in water (manufactured by Heraeus, Clevios F HC Solar) was applied to the formed active layer by spin coating to form a coating film. The glass substrate with the coating film formed on the active layer was placed in an oven and dried at 85°C for 30 minutes to form a second electrode. The thickness of the formed second electrode was about 120 nm.

[0356] (B-5. Formation of Encapsulation Layer) Next, an ultraviolet (UV) curable sealant was applied around the glass substrate on which the electrode (second electrode) was formed, and a glass plate was further bonded above the electrode, and then the sealant was cured and sealed by irradiating UV light to obtain a photoelectric conversion element. The obtained photoelectric conversion element had a square shape of 2 mm×2 mm.

[0357] By the above-described manufacturing method, a photoelectric conversion element B (light detection element B) in which a glass substrate, a first electrode, an electron transport layer, an active layer, and a second electrode are provided in this order can be manufactured.

[0358] [Evaluation of Photoelectric Conversion Element] The photoelectric conversion element manufactured by the manufacturing method A or the manufacturing method B was subjected to JV measurement in a dark place to obtain a dark current (Jd) at -5 V. A source meter (2450 model, manufactured by Keithley) was used for the JV measurement.

[0359] <Evaluation Results> The evaluation results are shown in the following table. In the following table, the relative values ​​of dark current (Jd) of evaluations 1 to 4 are relative values ​​when the dark current of evaluation 1 is 100. The relative values ​​of Jd of evaluations 5 to 6 are relative values ​​when the dark current of evaluation 5 is 100. The relative values ​​of Jd of evaluations 7 to 9 are relative values ​​when the dark current of evaluation 7 is 100. The relative values ​​of Jd of evaluations 10 to 11, evaluations 12 to 13, evaluations 14 to 15, evaluations 16 to 17, and evaluations 18 to 19 are relative values ​​when the dark current of evaluations 10, evaluation 12, evaluation 14, evaluation 16, and evaluation 18 are 100, respectively. In the following table, “element A” indicates photoelectric conversion element A manufactured according to manufacturing method A, and “element B” indicates photoelectric conversion element B manufactured according to manufacturing method B.

[0360] [Table 5]

[0361] The above results show that the dark current of the photoelectric conversion element including the active layer produced from the composition containing the surfactant is reduced compared with the photoelectric conversion element including the active layer produced from the composition not containing the surfactant. Furthermore, it was found that the photoelectric conversion element having an active layer produced from a composition containing a surfactant, regardless of the structure of the photoelectric conversion element A or the photoelectric conversion element B, had a reduced dark current.

Claims

1. A composition comprising a p-type semiconductor, an n-type semiconductor, a surfactant and a solvent. 2 . The composition according to claim 1 , wherein the p-type semiconductor is a polymer compound having a donor-acceptor structure.

3. The composition according to claim 1, wherein the p-type semiconductor is a polymer compound comprising one or more structural units selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II); In formula (I), Ar 1 and Ar 2 Each independently represents a trivalent aromatic heterocyclic group which may have a substituent, Z represents a group represented by any one of the following formulae (Z-1) to (Z-7); In formulae (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, a cycloalkenyl group which may be substituted, an alkynyl group which may be substituted, a cycloalkynyl group which may be substituted, an aryl group which may be substituted, an alkoxy group which may be substituted, a cycloalkyloxy group which may be substituted, an aryloxy group which may be substituted, an alkylthio group which may be substituted, a cycloalkylthio group which may be substituted, an arylthio group which may be substituted, a monovalent heterocyclic group which may be substituted, an amino group which may be substituted, an imine residue which may be substituted, an amide group which may be substituted, an imide group which may be substituted, a substituted oxycarbonyl group which may be substituted, a cyano group, a nitro group, -C(=O)-R c The group represented by -SO2-R d The group represented by R c and R d each independently represents a hydrogen atom, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an aryl group which may be substituted, an alkoxy group which may be substituted, a cycloalkoxy group which may be substituted, an aryloxy group which may be substituted, or a monovalent heterocyclic group which may be substituted, In formula (Z-1) to formula (Z-7), when there are two Rs, the two Rs are the same or different; Ar3(I I ) In formula (II), Ar 3 It represents a divalent aromatic heterocyclic group. The composition according to claim 1 , wherein the n-type semiconductor is a fullerene derivative. The composition according to claim 1 , wherein the n-type semiconductor is a non-fullerene compound. The composition according to claim 1 , wherein the solvent comprises an aromatic hydrocarbon solvent. The composition according to claim 1 , wherein the surfactant is a nonionic surfactant. The composition according to claim 1 , wherein the surfactant is a compound having a poly(meth)acrylate structure. 9 . The composition according to claim 1 , wherein the surfactant is a compound having an organopolysiloxane structure.

10. The composition according to claim 1, wherein the surfactant is a fluorine-based surfactant.

11. A film comprising a p-type semiconductor, an n-type semiconductor and a surfactant.

12. An organic photoelectric conversion element comprising a first electrode, the film according to claim 11, and a second electrode in this order. 13 . A light detection element comprising the organic photoelectric conversion element according to claim 12 .

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