Composition, and method for producing film, organic photoelectric conversion element, and photodetection element

Abstract

To provide a composition with which an organic photoelectric conversion element with less variation in characteristics can be produced.SOLUTION: A composition includes a p-type semiconductor material, an n-type semiconductor material, an insulation material and a solvent, in which the p-type semiconductor material includes a polymer comprising a constitutional unit represented by formula (I). (In formula (I), Ar1 and Ar2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent. Z represents a group represented by formula (Z-1) to formula (Z-4). (In formula (Z-1) to (Z-4), R represents a hydrogen atom or the like, and two Rs in the formulas may be identical to or different from each other.))SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Photoelectric conversion elements including organic films have attracted attention, for example, as extremely useful power generation devices from the viewpoints of energy saving and reducing carbon dioxide emissions, or as light detection elements in photosensors highly sensitive to near-infrared rays.

[0003] A composition containing a p-type semiconductor material, a fullerene compound which is an n-type semiconductor material, and a specific additive is known as a composition for forming an active layer of an organic photoelectric conversion element (Patent Document 1). It is disclosed that adding a polymer other than the semiconductor material to the composition is effective as a means for obtaining a composition with viscosity properties suitable for the coating film formation process of the active layer in the production of an organic electronic device. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2018-525487 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, in the manufacture of an optical sensor including a photoelectric conversion element, a device having a structure in which patterned electrodes, an active layer, etc. are laminated on a single substrate, and a plurality of photoelectric conversion elements are arranged on the single substrate is usually used. Here, the active layer is required to have a certain degree of thickness in order to suppress dark current, which becomes noise in sensor performance, and a uniformity in film thickness so that the characteristics of each element do not vary. As a method for easily manufacturing an active layer with a uniform film thickness, a spin coating method is often used. The inventors attempted to form an active layer by a spin coating method using a composition containing an additive with reference to Patent Document 1. As a result, the desired uniform and thick active layer was obtained, but it was found that the device contained many defective elements with abnormally high dark currents, and that there was a large variation in dark current characteristics between elements contained in the device.

[0006] Therefore, there is a demand for a composition that can be used to produce an organic photoelectric conversion element with little variation in dark current characteristics; a film that can be produced from the composition; an organic photoelectric conversion element including the film; and a light detection element including the organic photoelectric conversion element. [Means for solving the problem]

[0007] As a result of intensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by forming an active layer using a composition containing a specific p-type semiconductor material and an insulating material in combination, and have completed the present invention.

[0008] [1] A composition comprising a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, The composition, wherein the p-type semiconductor material comprises a polymer containing a constitutional unit represented by the following formula (I): [ka] (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 the following formulae (Z-1) to (Z-4). [ka] (In formulas (Z-1) to (Z-4), R is Hydrogen atoms, Halogen atoms, 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 optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; Cyano group, Nitro group, -C(=O)-R a or -SO2-R b represents a group represented by R a and R b are each independently Hydrogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent. In formulas (Z-1) to (Z-4), the two R's may be the same or different. [2] The composition according to [1], wherein the insulating material is a material that dissolves in the solvent at 25°C at a concentration of 0.1% by weight or more. [3] The composition according to [1] or [2], wherein the insulating material comprises a polymer containing a constitutional unit represented by the following formula (II): [ka] (In formula (II), R i1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, R i2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by formula (III-2), or a group represented by formula (III-3). [ka] (In formula (III-1), Multiple R's i2a each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. [ka] (In formula (III-2), R i2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. [ka] (In formula (III-3), R i2c represents an alkyl group having 1 to 20 carbon atoms. [4] A semiconductor device comprising a p-type semiconductor material, an n-type semiconductor material, and an insulating material; The p-type semiconductor material comprises a polymer containing a constitutional unit represented by the following formula (I): [ka] (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 the following formulae (Z-1) to (Z-4). [ka] (In formulas (Z-1) to (Z-4), R is Hydrogen atom, Halogen atoms, 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 optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; Cyano group, Nitro group, -C(=O)-R a or -SO2-R b represents a group represented by R a and R b are each independently Hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent. In formulas (Z-1) to (Z-4), the two R's may be the same or different. [5] An organic photoelectric conversion element comprising a first electrode, the film according to [4], and a second electrode in this order. [6] A photodetector comprising the organic photoelectric conversion element according to [5]. Effect of the Invention

[0009] According to the present invention, there are provided a composition capable of producing an organic photoelectric conversion element having small variation in dark current characteristics; a film that can be produced from the composition; an organic photoelectric conversion element including the film; and a light detection element including the organic photoelectric conversion element. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram illustrating a schematic configuration example of a photoelectric conversion element. [Diagram 2] FIG. 2 is a diagram illustrating a schematic configuration example of the image detection unit. [Diagram 3] FIG. 3 is a diagram illustrating a schematic configuration example of the fingerprint detection unit. [Figure 4] FIG. 4 is a diagram illustrating a schematic configuration example of an image detection unit for an X-ray imaging device. [Diagram 5] FIG. 5 is a diagram illustrating a configuration example of a vein detection unit for use in a vein authentication device. [Figure 6] FIG. 6 is a diagram showing a schematic configuration example of an image detection unit for an indirect type TOF distance measuring device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Explanation of common terms] First, terms commonly used in the following description will be explained. "Polymer compounds" are compounds that have a molecular weight distribution and have a number average molecular weight of 1×10 3 More than 1×10 8 The term "polymer" refers to a polymer having the following structure: The structural units contained in the polymer total 100 mol %.

[0012] The term "structural unit" refers to a structural unit that a polymer has.

[0013] The "hydrogen atom" may be a protium atom or a deuterium atom.

[0014] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0015] The embodiment in which "optionally has a substituent" includes both the case in which all hydrogen atoms constituting the compound or group are unsubstituted, and the case in which one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0016] Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an alkyloxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group.

[0017] The "alkyl group" may be linear or branched. The alkyl group may have a substituent. The number of carbon atoms of the alkyl group is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20, not including the number of carbon atoms of the substituent.

[0018] Examples of the alkyl group include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-ethylbutyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 3-propylheptyl, n-decyl, 3,7-dimethyloctyl, 3-heptyldodecyl, 2-ethyloctyl, 2-hexyldecyl, dodecyl, n-tetradecyl, hexadecyl, octadecyl, and icosyl, as well as groups in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

[0019] Specific examples of the alkyl having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3-(4-methylphenyl)propyl group, a 3-(3,5-dihexylphenyl)propyl group, and a 6-ethyloxyhexyl group.

[0020] The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group is usually 3 to 30, preferably 3 to 20, not including the number of carbon atoms in the substituent.

[0021] Examples of cycloalkyl groups include unsubstituted alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group, as well as groups in which the hydrogen atoms in these groups are substituted with substituents such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0022] Specific examples of the substituted cycloalkyl group include a methylcyclohexyl group and an ethylcyclohexyl group.

[0023] The "alkenyl group" may be linear or branched. The alkenyl group may have a substituent. The number of carbon atoms in the alkenyl group is usually 2 to 30, preferably 2 to 20, not including the number of carbon atoms in the substituent.

[0024] Examples of the alkenyl group 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, as well as groups in which the hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups, and fluorine atoms.

[0025] 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 is usually 3 to 30, preferably 3 to 20, not including the number of carbon atoms of the substituent.

[0026] Examples of the cycloalkenyl group include unsubstituted cycloalkenyl groups, such as a cyclohexenyl group, and groups in which a hydrogen atom in such a group is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0027] Examples of the substituted cycloalkenyl group include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0028] The "alkynyl group" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms in the alkynyl group is usually 2 to 30, preferably 2 to 20, not including the number of carbon atoms in the substituent.

[0029] Examples of the alkynyl group include unsubstituted alkynyl groups such as ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, and 5-hexynyl groups, as well as groups in which the hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups, and fluorine atoms.

[0030] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group is usually 4 to 30, preferably 4 to 20, not including the number of carbon atoms in the substituent.

[0031] Examples of the cycloalkynyl group include unsubstituted cycloalkynyl groups, such as a cyclohexynyl group, and groups in which the hydrogen atoms in these groups are substituted with substituents such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0032] Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0033] The "alkyloxy group" may be linear or branched. The alkyloxy group may have a substituent. The number of carbon atoms in the alkyloxy group is usually 1 to 30, preferably 1 to 20, not including the number of carbon atoms in the substituent.

[0034] Examples of the alkyloxy group include unsubstituted alkyloxy groups such as a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group, an n-decyloxy group, a 3,7-dimethyloctyloxy group, a 3-heptyldodecyloxy group, and a lauryloxy group, as well as groups in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

[0035] The cycloalkyl group in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group is usually 3 to 30, preferably 3 to 20, not including the number of carbon atoms in the substituent.

[0036] Examples of the cycloalkyloxy group include unsubstituted cycloalkyloxy groups, such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group, as well as groups in which the hydrogen atom in these groups is substituted with a substituent such as a fluorine atom or an alkyl group.

[0037] The "alkylthio group" may be linear or branched. The alkylthio group may have a substituent. The number of carbon atoms of the alkylthio group is usually 1 to 30, preferably 1 to 20, not including the number of carbon atoms of the substituent.

[0038] 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-ethylhexylthio 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.

[0039] The cycloalkyl group of the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms of the cycloalkylthio group is usually 3 to 30, preferably 3 to 20, not including the number of carbon atoms of the substituent.

[0040] An example of the optionally substituted cycloalkylthio group is a cyclohexylthio group.

[0041] The term "p-valent aromatic carbocyclic group" refers to the atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent. The p-valent aromatic carbocyclic group may further have a substituent.

[0042] The term "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 is usually 6 to 60, preferably 6 to 48, not including the carbon atoms of the substituent.

[0043] Examples of the aryl group include unsubstituted aryl groups such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, and a 4-phenylphenyl group, as well as groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0044] The "aryloxy group" may have a substituent. The number of carbon atoms of the aryloxy group is usually 6 to 60, and preferably 6 to 48, not including the number of carbon atoms of the substituent.

[0045] Examples of the aryloxy group include unsubstituted aryloxy groups such as a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, and a 1-pyrenyloxy group, as well as groups in which the hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0046] The "arylthio group" may have a substituent. The number of carbon atoms of the arylthio group is usually 6 to 60, and preferably 6 to 48, not including the number of carbon atoms of the substituent.

[0047] Examples of the arylthio group which may have a substituent include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group. "C1-C12" indicates that the group described immediately after has 1 to 12 carbon atoms. Furthermore, "Cm-Cn" indicates that the group described immediately after has m to n carbon atoms. The same applies below.

[0048] A "p-valent heterocyclic group" (p represents an integer of 1 or greater) refers to the atomic group remaining after removing p hydrogen atoms from among the hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring of an optionally substituted heterocyclic compound. A "p-valent heterocyclic group" includes a "p-valent aromatic heterocyclic group." A "p-valent aromatic heterocyclic group" refers to the atomic group remaining after removing p hydrogen atoms from among the hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring of an optionally substituted aromatic heterocyclic compound.

[0049] The aromatic heterocyclic compounds include compounds in which the heterocycle itself exhibits aromaticity, as well as compounds in which an aromatic ring is condensed with a heterocycle even if the heterocycle itself does not exhibit aromaticity.

[0050] Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

[0051] Specific examples of aromatic heterocyclic compounds in which the heterocycle itself does not exhibit aromaticity and an aromatic ring is condensed with the heterocycle include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0052] The p-valent heterocyclic group may have a substituent. The number of carbon atoms in the p-valent heterocyclic group is usually 2 to 60, and preferably 2 to 20, not including the number of carbon atoms in the substituent.

[0053] Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (e.g., thienyl, pyrrolyl, furyl, pyridyl, quinolyl, isoquinolyl, pyrimidinyl, and triazinyl groups), monovalent non-aromatic heterocyclic groups (e.g., piperidyl and piperazyl groups), and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.

[0054] The term "substituted amino group" refers to an amino group having a substituent. The substituent of the amino group is preferably an alkyl group, an aryl group, or a monovalent heterocyclic group. The number of carbon atoms of the substituted amino group is usually 2 to 30, not including the number of carbon atoms of the substituent.

[0055] Examples of the substituted amino group include dialkylamino groups (e.g., dimethylamino group, diethylamino group), and diarylamino groups (e.g., diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl)amino group, bis(3,5-di-tert-butylphenyl)amino group).

[0056] The "acyl group" may have a substituent. The number of carbon atoms of the acyl group, not including the number of carbon atoms of the substituent, is usually 2 to 20, and preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

[0057] The term "imine residue" refers to the remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon-nitrogen double bond from an imine compound. The term "imine compound" refers to an organic compound having a carbon-nitrogen double bond in the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atom bonded to the nitrogen atom constituting the carbon-nitrogen double bond in an aldimine is substituted with an alkyl group or the like.

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

[0059] [ka]

[0060] The term "amide group" refers to an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an amide. The number of carbon atoms in the amide group is usually 1 to 20, and preferably 1 to 18. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

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

[0062] [ka]

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

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

[0065] Specific examples of the substituted oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl group, a dodecyloxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.

[0066] The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group is usually 1 to 30, not including the number of carbon atoms in the substituent. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0067] The "*" in a chemical formula represents a bond.

[0068] "π-conjugated system" means a system in which the π-electrons are delocalized among multiple bonds.

[0069] The term "(meth)acrylic" includes acrylic, methacrylic, and combinations thereof.

[0070] [1. Composition] A composition according to one embodiment of the present invention includes a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, and the p-type semiconductor material includes a polymer including a structural unit represented by formula (I). By using such a composition, an organic photoelectric conversion element having small variation in dark current characteristics can be manufactured.

[0071] Although the details of the mechanism by which the composition of the present invention suppresses the variation in dark current characteristics are unclear, the following mechanism is considered, but the present invention is not limited thereto. In the composition of the present invention, by including an insulating material that is not directly involved in the photoelectric conversion effect as an additive, the concentration and viscosity properties of the composition can be properly adjusted, and a coating film of uniform thickness can be produced during coating. On the other hand, since the solid content concentration and viscosity of the composition are increased by adding an insulating material, it is considered that the aggregation of the p-type semiconductor material and the n-type semiconductor material is likely to proceed during the process of coating and drying the composition. In particular, from the viewpoint of light absorption and charge transport properties, many polymers used as p-type semiconductor materials have a planar and symmetrical molecular structure with continuous π conjugation. Therefore, it is considered that crystallization and crystal growth are likely to proceed during the process of coating and drying. In an active layer containing a polymer that is a p-type semiconductor material having such a molecular structure, it is presumed that large crystals of the p-type semiconductor material are included, and pinholes and local thinning starting from these crystals occur. On the other hand, the polymer containing the constitutional unit represented by formula (I), which is a p-type semiconductor material, contained in the composition of the present invention has an asymmetric molecular structure. Therefore, it is considered that the polymer is unlikely to crystallize during the coating and drying process, and is present in the active layer as fine particles. As a result, it is considered that defects such as fine pinholes and thinning caused by large particles in the composition are unlikely to occur in the active layer obtained from the composition of the present invention, and it is presumed that the element obtained from the composition of the present invention has excellent uniformity in dark current characteristics.

[0072] In the composition, the p-type and n-type semiconductor materials may be dissolved or dispersed. The p-type and n-type semiconductor materials are preferably at least partially dissolved, and more preferably completely dissolved.

[0073] [1.1. p-type semiconductor materials] The p-type semiconductor material according to this embodiment includes a polymer containing a constitutional unit represented by the following formula (I). Hereinafter, the polymer containing the constitutional unit represented by formula (I) is also referred to as polymer (1). The p-type semiconductor material may contain only one type of polymer (1), or may contain two or more types. Furthermore, the polymer (1) may contain only one type of constitutional unit represented by formula (I), or may contain two or more types. [ka]

[0074] 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 the following formulae (Z-1) to (Z-4).

[0075] [ka]

[0076] In the formulas (Z-1) to (Z-4), R is Hydrogen atoms, Halogen atoms, 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 optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; Cyano group, Nitro group, -C(=O)-R a or -SO2-R b represents a group represented by R a and R b are each independently Hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent. In formulae (Z-1) to (Z-4), the two R's may be the same or different.

[0077] Ar 1 Or Ar 2Examples of aromatic heterocycles constituting the trivalent aromatic heterocycle group represented by include oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, pyrrole ring, phosphole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphole ring, as well as phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring.These rings may have a substituent.

[0078] Z is preferably a group represented by formula (Z-1) or (Z-2).

[0079] R in the formulas (Z-1) to (Z-4) is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, even more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have a substituent. A plurality of R may be the same or different.

[0080] In one embodiment, the constitutional unit represented by formula (I) is preferably a constitutional unit represented by the following formula (I-1) or (I-2).

[0081] [ka]

[0082] In formula (I-1) and formula (I-2), X 1 and X 2 are each independently a sulfur atom or an oxygen atom; Z 1 and Z 2 are each independently a group represented by =C(R)- or a nitrogen atom, and R is the same as defined in formulae (Z-1) to (Z-4). A plurality of R may be the same or different.

[0083] The structural unit represented by formula (I-1) is X 1 and X 2 is a sulfur atom, and Z 1 and Z 2 is preferably a structural unit in which Z is a group represented by =C(R)-. 1 and Z 2 R in the group represented by =C(R)- as above is preferably a hydrogen atom. The structural unit represented by formula (I-2) is X 1 and X 2 is a sulfur atom, and Z 1 and Z 2 is preferably a structural unit in which Z is a group represented by =C(R)-. 1 and Z 2 R in the group represented by =C(R)- as above is preferably a hydrogen atom.

[0084] Examples of the structural unit (I-1) include structural units represented by the following formulae (I-1-1) to (I-1-14). In the following formulae (I-1-1) to (I-1-14), R is defined as in the formulae (Z-1) to (Z-4). Multiple R may be the same or different. Of these, the structural unit represented by formula (I-1-1) is preferred.

[0085] [ka]

[0086] Examples of the structural unit (I-2) include structural units represented by the following formulae (I-2-1) to (I-2-14). In the following formulae (I-2-1) to (I-2-14), R is defined as in the formulae (Z-1) to (Z-4). Multiple R may be the same or different. Of these, the structural unit represented by formula (I-2-1) is preferred.

[0087] [ka]

[0088] The polymer (1) preferably contains a structural unit represented by formula (IV) in addition to the structural unit represented by formula (I). The polymer (1) may contain only one type of structural unit represented by formula (IV), or may contain two or more types of structural units represented by formula (IV).

[0089] -Ar 3 - (IV)

[0090] In formula (IV), Ar 3 represents a divalent aromatic heterocyclic group.

[0091] Ar 3 The number of carbon atoms in the divalent aromatic heterocyclic group represented by the following formula is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20. 3 The divalent aromatic heterocyclic group represented by the following formula (I) may have a substituent. The constitutional unit represented by formula (IV) is preferably a constitutional unit represented by any one of the following formulae (IV-1) to (IV-8).

[0092] [ka]

[0093] In formulas (IV-1) to (IV-8), X 1 , X 2 , Z 1 , Z 2 and R are the same as defined in formula (I-1) and formula (I-2). When there are two R, the two R may be the same or different. In formula (IV-6), the two R's are preferably each independently a hydrogen atom, an alkyl group, or a halogen atom, more preferably both a hydrogen atom or a halogen atom, and even more preferably both a halogen atom.

[0094] From the viewpoint of availability of raw material compounds, X in formulas (IV-1) to (IV-8) 1 and X 2are preferably sulfur atoms.

[0095] Ar 3 Specific examples of the divalent aromatic heterocyclic group represented by the formula (101) include groups represented by the following formulas (101) to (190) and groups in which these groups are substituted with a substituent. Preferred as the substituent are halogen atoms and alkyl groups. Among them, preferred are groups represented by formula (148) or formula (190).

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] In the formulae (101) to (190), R has the same meaning as defined above. When there are multiple R, the multiple R may be the same or different.

[0101] The total amount of the constitutional unit represented by formula (I) and the constitutional unit represented by formula (IV) in polymer (1) is preferably 20 mol% to 100 mol%, assuming that the amount of all constitutional units contained in polymer (1) is 100 mol%, and since the charge transport property as a p-type semiconductor material can be improved, it is more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%. Here, when polymer (1) does not contain the constitutional unit represented by formula (IV), the total amount of the constitutional unit represented by formula (I) and the constitutional unit represented by formula (IV) is the amount of the constitutional unit represented by formula (I).

[0102] Preferably, the polymer (1) contains any combination of the following structural units: A combination of a structural unit represented by formula (I-2) and a structural unit represented by formula (IV-6) A combination of a structural unit represented by formula (I-2) and a structural unit represented by formula (IV-8)

[0103] More preferably, the polymer (1) contains any of the following combinations of structural units: A combination of a structural unit represented by formula (I-2-1) and a structural unit represented by formula (148) A combination of a structural unit represented by formula (I-2-1) and a structural unit represented by formula (190)

[0104] Specific examples of the polymer (1) that is the p-type semiconductor material in this embodiment include polymers represented by the following formulas (P-1) and (P-2).

[0105] [ka]

[0106] The weight proportion of polymer (1) in the p-type semiconductor material is preferably 20% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more, and is usually 100% by weight or less, and may be 100% by weight.

[0107] The composition of the present embodiment may contain, in addition to the polymer (1), any other compound as a p-type semiconductor material. Examples of other compounds that are p-type semiconductor materials include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylenevinylene and its derivatives, polythienylenevinylene and its derivatives, and polyfluorene and its derivatives. The composition according to this embodiment may contain only one or more other compounds as p-type semiconductor materials in addition to the polymer (1).

[0108] [1.2. n-type semiconductor materials] The composition according to the present embodiment includes an n-type semiconductor material. The composition according to the present embodiment may include only one type of compound as the n-type semiconductor material, or may include multiple types of compounds. Many types of compounds are known as n-type semiconductor materials, and they can be used as the n-type semiconductor material according to the present embodiment.

[0109] Whether the semiconductor material contained in the composition functions as a p-type semiconductor material or an n-type semiconductor material can be determined relatively from the HOMO energy level value or the LUMO energy value of the selected compound. The relationship between the HOMO and LUMO energy level values ​​of the p-type semiconductor material and the HOMO and LUMO energy level values ​​of the n-type semiconductor material can be appropriately set within a range in which the film produced from the composition exhibits a desired function (e.g., photoelectric conversion function, photodetection function).

[0110] The n-type semiconductor material according to this embodiment may be a low molecular weight compound or a high molecular weight compound. Examples of n-type semiconductor materials (electron-accepting compounds) include C 60Examples of such compounds include fullerenes and derivatives thereof, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and phenanthrene derivatives such as bathocuproine.

[0111] In one embodiment, the composition may include a fullerene or a fullerene derivative as the n-type semiconductor material. An example of a fullerene is C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene and C 84 Fullerenes are an example.

[0112] Examples of the fullerene derivative include the compounds represented by the following formulas (F-1) to (F-4).

[0113] [ka]

[0114] In formulas (F-1) to (F-4), R X represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. X may be the same or different from each other. R Y represents an alkyl group or an aryl group. Y may be the same or different from each other.

[0115] R X Examples of the monovalent heterocyclic group represented by the formula (I) include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.

[0116] R X Examples of the group having an ester structure represented by the formula (E-1) include a group represented by the formula (E-2).

[0117] [ka]

[0118] (In the formula, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R Z represents an alkyl group, an aryl group, or a monovalent heterocyclic group.

[0119] C 60 Examples of fullerene derivatives include the following compounds: wherein R is as defined above.

[0120] [ka]

[0121] C 70 Examples of fullerene derivatives include the following compounds:

[0122] [ka]

[0123] Specific examples of fullerene derivatives include [6,6]-phenyl-C61 butyric acid methyl ester (C60PCBM), [6,6]-phenyl-C71 butyric acid methyl ester (C70PCBM), [6,6]-Phenyl C71 butyric acid methyl ester (C84PCBM), [6,6]-Phenyl C85 butyric acid methyl ester, and [6,6]-Thienyl C61 butyric acid methyl ester.

[0124] The n-type semiconductor material according to this embodiment may contain a compound that is neither a fullerene nor a derivative of a fullerene. Hereinafter, a compound that is neither a fullerene nor a derivative of a fullerene is also referred to as a non-fullerene compound.

[0125] In one embodiment, the n-type semiconductor material preferably includes a compound represented by the following formula (V): A 1 -B 10 -A 2 (V)

[0126] In formula (V), A 1 and A 2 each independently represents an electron-withdrawing group; B 10 represents a group containing a π-conjugated system.

[0127] 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).

[0128] [ka]

[0129] In formulas (a-1) to (a-7), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring may be a single ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.

[0130] Examples of the carbocyclic ring which may have a substituent which is T include aromatic carbocyclic rings, preferably aromatic carbocyclic rings. Specific examples of the carbocyclic ring which may have a substituent which is T include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, preferably a benzene ring, a naphthalene ring, and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have a substituent.

[0131] Examples of the heterocycle that may have a substituent that is T include aromatic heterocycles, and preferably aromatic heterocycles. Specific examples of the heterocycle that may have a substituent that is 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, and preferably thiophene ring, pyridine ring, pyrazine ring, thiazole ring, and thienothiophene ring, and more preferably thiophene ring. These rings may have a substituent.

[0132] Examples of the substituent that the carbocycle or heterocycle represented by T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, and a monovalent heterocyclic group, and preferably a fluorine atom and / or an alkyl group having 1 to 6 carbon atoms.

[0133] X 4 , X 5 , and X 6 each independently represents an oxygen atom, a sulfur atom, an alkylidene group, or a group represented by =C(-CN)2, and is preferably an oxygen atom, a sulfur atom, or a group represented by =C(-CN)2.

[0134] X 7 represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or a monovalent heterocyclic group.

[0135] R a1 , R a2 , R a3 , R a4 , and R a5 each independently represents a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyloxy group, an optionally substituted aryl group, or a monovalent heterocyclic group, and is preferably an optionally substituted alkyl group or an optionally substituted aryl group.

[0136] [ka]

[0137] In formula (a-8) and formula (a-9), R a6 and R a7 each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted monovalent aromatic carbocyclic group, or an optionally substituted monovalent aromatic heterocyclic group; a6 and R a7 may be the same or different.

[0138] A 1 and A 2 The electron-withdrawing group represented by R is preferably a group represented by any one of the following formulae (a-1-1) to (a-1-4), (a-6-1) and (a-7-1), and more preferably a group represented by formula (a-1-1). a10 R 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.

[0139] [ka]

[0140] B 10 Examples of the group containing a π-conjugated system include -(S 1 ) n1 -B 11 -(S 2 ) n2 - is an example of a group represented by the formula:

[0141] In one embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VI): A 1 -(S 1 ) n1 -B 11 -(S 2 ) n2 -A 2 (VI)

[0142] In formula (VI), A 1 and A 2 Each independently represents an electron-withdrawing group. 1 and A 2 Examples and preferred examples of the above are A 1 and A 2 This is similar to the examples and preferred examples described above.

[0143] 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 )- (wherein R s1 and R s2 each independently represents a hydrogen atom, a substituent (preferably a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or an optionally substituted monovalent heterocyclic group), or a group represented by -C≡C-.

[0144] S 1 and S 2 The optionally substituted divalent carbocyclic group and optionally substituted divalent heterocyclic group represented by the following formula may be a condensed ring. When the divalent carbocyclic group or divalent heterocyclic group has multiple substituents, the multiple substituents may be the same or different.

[0145] In formula (VI), n1 and n2 each independently represent an integer of 0 or more, preferably each independently represent 0 or 1, and more preferably simultaneously represent 0 or 1.

[0146] Examples of divalent carbocyclic groups include divalent aromatic carbocyclic groups. Examples of the divalent heterocyclic group include a divalent aromatic heterocyclic group. When the divalent aromatic carbocyclic group or divalent aromatic heterocyclic group is a fused ring, all of the rings constituting the fused ring may be fused rings having aromaticity, or only some of the fused rings may be fused rings having aromaticity.

[0147] S 1 and S 2 An example of this is the already mentioned Ar 3 Examples of the divalent aromatic heterocyclic group represented by the formula (101) to (190) given above include groups represented by the formula (101) to (190), and these groups in which hydrogen atoms are substituted with substituents.

[0148] S 1 and S 2 preferably each independently represents a group represented by the following formula (s-1) or (s-2).

[0149] [ka]

[0150] In formulas (s-1) and (s-2), X 3 represents an oxygen atom or a sulfur atom. R a10 is as defined above.

[0151] S 1 and S 2 are preferably, each independently, a group represented by formula (142), formula (148), or formula (184), or a group in which a hydrogen atom in these groups is substituted with a substituent, and more preferably a group represented by formula (142) or formula (184), or a group in which one hydrogen atom in the group represented by formula (184) is substituted with an alkyloxy group.

[0152] B 11 represents a fused ring group having two or more structures selected from the group consisting of carbocyclic structures and heterocyclic structures, which does not contain an ortho-peri fused structure and which may have a substituent.

[0153] B 11 The fused ring group represented by the following formula may include a structure in which two or more identical structures are fused together.

[0154] B 11 When the fused ring group represented by the following formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

[0155] B 11 Examples of the carbocyclic structure that can constitute the fused ring group represented by the following formula (Cy1) or (Cy2) include ring structures represented by the following formula (Cy1) or (Cy2).

[0156] [ka]

[0157] B 11 Examples of the heterocyclic structure that can constitute the fused ring group represented by the following formula (Cy3) to formula (Cy10) include ring structures represented by any of the following formulas (Cy3) to (Cy10).

[0158] [ka]

[0159] In formula (VI), B 11 is preferably a fused ring group having two or more structures selected from the group consisting of structures represented by the above formulae (Cy1) to (Cy10), which does not contain an ortho-peri fused structure and which may have a substituent. 11 may contain a structure in which two or more identical structures among the structures represented by formulae (Cy1) to (Cy10) are condensed.

[0160] B 11 is more preferably a fused ring group having two or more structures selected from the group consisting of structures represented by formulae (Cy1) to (Cy6) and (Cy8), which is a fused ring group not containing an ortho-peri fused structure and which may have a substituent.

[0161] 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 alkyloxy group that may have a substituent, or a monovalent heterocyclic group that may have a substituent. 11 The aryl group which the fused ring group represented by the following formula (I) may have may be substituted with, for example, an alkyl group.

[0162] B 11 Examples of the fused ring group include groups represented by the following formulas (b-1) to (b-14), and groups in which a hydrogen atom in these groups is substituted with a substituent (preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent). B 11The fused ring group represented by the formula (b-4) below is preferably a group represented by the formula (b-4) below, or a group in which a hydrogen atom in such a group is substituted with a substituent (preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent), and more preferably a group represented by the formula (b-4) below.

[0163] [ka]

[0164] [ka]

[0165] In formulas (b-1) to (b-14), R a10 is as defined above. In the formulas (b-1) to (b-14), there are multiple R a10 are each independently preferably an alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0166] Examples of the compound represented by formula (V) or formula (VI) include compounds represented by the following formulas:

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171]

change

[0172]

change

[0173]

change

[0174]

change

[0175]

change

[0176]

change

[0177]

change

[0178]

change

[0179]

change

[0180]

change

[0181] [ka]

[0182] 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 optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkyloxy group.

[0183] The compound represented by formula (V) or (VI) includes the compound represented by the following formula N-1.

[0184] [ka]

[0185] In one embodiment, the n-type semiconductor material is preferably a compound containing a perylene tetracarboxylic diimide structure. Examples of the compound containing a perylene tetracarboxylic diimide structure as a non-fullerene compound include the compound represented by the following formula:

[0186] [ka]

[0187] [ka]

[0188] [ka]

[0189] In the formula, R is as defined above. A plurality of R may be the same or different.

[0190] In one embodiment, the n-type semiconductor material preferably includes a compound represented by the following formula (VII): The compound represented by the following formula (VII) is a non-fullerene compound including a perylene tetracarboxylic diimide structure.

[0191] [ka]

[0192] In the formula (VII), R 1 represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group. 1 may be the same or different from each other.

[0193] Preferably, there are multiple R 1 each independently represents an alkyl group which may have a substituent.

[0194] R 2 represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group. 2 may be the same or different.

[0195] [1.3. Insulating materials] The composition of the present embodiment includes an insulating material. Here, the insulating material means a material that is neither a conductor nor a semiconductor. Generally, an insulating material has an electrical resistivity of 1×10 at 20° C. 7 Ω·m or more. Insulating materials are usually not involved in the photoelectric conversion process.

[0196] The insulating material is preferably an organic compound, more preferably an organic polymer, and may contain only one type of organic compound or a combination of two or more types of organic compounds.

[0197] Various organic compounds are known as insulating materials and may be used in the composition of the present embodiment. Examples of organic polymers that are insulating materials include polyolefins (e.g., polyethylene, polypropylene, poly(1-butene), polyisobutylene), poly(aromatic vinyl)s (e.g., polystyrene and its derivatives), poly(methyl (meth)acrylate, polyester, polyvinyl carboxylate, polyvinyl acetal, polycarbonate, polyurethane, polyarylate, polyamide, polyimide, cellulose and its derivatives, polysiloxane, rubber, and thermoplastic elastomers. The organic polymer that can be included in the insulating material may be a homopolymer or a copolymer.

[0198] The insulating material preferably contains a polymer containing a structural unit represented by the following formula (II). Hereinafter, the polymer containing the structural unit represented by formula (II) is also referred to as polymer (2). Polymer (2) may contain only one type of structural unit represented by formula (II), or may contain two or more types in combination.

[0199] [ka]

[0200] In formula (II), R i1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms; R i2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by formula (III-2), or a group represented by formula (III-3).

[0201] [ka]

[0202] In the formula (III-1), R i2a represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. In the formula (III-2), R i2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In the formula (III-3), R i2c represents an alkyl group having 1 to 20 carbon atoms.

[0203] R i1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom.

[0204] R i2a is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom.

[0205] R i2b is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.

[0206] R i2c is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.

[0207] R i2 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by formula (III-1) to formula (III-3), more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (III-1) to formula (III-3), and even more preferably an alkyl group having 1 to 5 carbon atoms, or a group represented by formula (III-1) to formula (III-3).

[0208] In one embodiment, the polymer (2) is represented by the formula (II), R i2 is an alkyl group having 1 to 20 carbon atoms, and in formula (II), R i2 It is preferable that the structural unit represented by the formula (III-1) contains one or more structural units selected from the group consisting of structural units represented by the formula (III-2), and the structural unit represented by the formula (II) is polystyrene or a styrene unit and R i2 It is more preferable that the polymer is a polymer containing a structural unit represented by formula (III-1). In another embodiment, the polymer (2) is represented by the formula (II) R i2 preferably contains a structural unit represented by formula (III-2), and more preferably contains a methyl methacrylate unit.

[0209] The content of polymer (2) in the insulating material is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more, and usually 100% by weight or less, and may be 100% by weight. The insulating material may contain only one type of polymer (2) or a combination of two or more types.

[0210] Polymer (2) may contain any structural unit in addition to the structural unit represented by formula (II). Examples of the optional structural unit include an alkadiene unit (e.g., 1,3-butadiene unit, isoprene unit).

[0211] The polymer (2) can be produced by a conventionally known production method. Alternatively, a commercially available product can be used as the polymer (2).

[0212] Preferably, the insulating material is a material that dissolves at 25° C. in a solvent used in the composition of the present invention at a concentration of 0.1% by weight or more. More preferably, the insulating material is the polymer (2), which is soluble in the solvent used in the composition of the present invention at 25° C. in an amount of 0.1% by weight or more.

[0213] The weight average molecular weight (Mw) of the organic polymer that can be contained in the insulating material is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less.

[0214] Specific examples of insulating materials according to this embodiment include polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (weight average molecular weight: 118,000 or less), polystyrene (weight average molecular weight: 35,000), polystyrene-block-polyisoprene-block-polystyrene (number average molecular weight 1900), and poly(methyl methacrylate).

[0215] The content of the insulating material in the composition is, for example, 0.5% by weight or more, or 0.1% by weight or more, and, for example, 5% by weight or less, or 1% by weight or less, where the total weight of the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent in the composition is taken as 100% by weight.

[0216] The insulating material is preferably at least partially dissolved in the composition, and more preferably completely dissolved.

[0217] In the composition, the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) is, for example, 1 / 10 or more or 1 / 5 or more, and for example, 1 / 3 or less or 1 / 2 or less.

[0218] [1.4. Solvent] The composition according to the present embodiment includes a solvent. The composition may include only one type of solvent, or may include two or more types of solvents in combination. The composition according to this embodiment preferably contains a first solvent described below, and may optionally further contain a second solvent.

[0219] (First Solvent) The solvent may be selected in consideration of the solubility of the selected p-type and n-type semiconductor materials, and the properties (boiling point, etc.) required to meet the drying conditions when forming a film.

[0220] The first solvent is preferably an aromatic hydrocarbon (hereinafter simply referred to as aromatic hydrocarbon) which may have a substituent (e.g., an alkyl group, a halogen atom) or an alkyl halide solvent. The first solvent is preferably selected in consideration of the solubility of the selected p-type semiconductor material and n-type semiconductor material.

[0221] Examples of aromatic hydrocarbons that are the first solvent include toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), trimethylbenzene (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), tetralin, indane, chlorobenzene, and dichlorobenzene (1,2-dichlorobenzene).

[0222] The first solvent, ie, the alkyl halide solvent, may, for example, be chloroform.

[0223] The first solvent may be composed of only one type of aromatic hydrocarbon, or may be composed of two or more types of aromatic hydrocarbons, but is preferably composed of only one type of aromatic hydrocarbon.

[0224] The first solvent preferably includes one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, pseudocumene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, indane, chlorobenzene, o-dichlorobenzene, and chloroform.

[0225] (Second Solvent) The second solvent is preferably a solvent selected from the viewpoint of increasing the solubility of the n-type semiconductor material. Examples of the second solvent include ketone solvents (e.g., acetone, methyl ethyl ketone, cyclohexanone, acetophenone, propiophenone) and ester solvents (e.g., ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate, benzyl benzoate).

[0226] (Weight ratio of first solvent to second solvent) When the composition contains the first solvent and the second solvent, the weight ratio of the first solvent to the second solvent (first solvent / second solvent) is preferably in the range of 85 / 15 to 99 / 1, from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material.

[0227] (Weight Percentage of Solvent in Composition) The total weight of the solvent contained in the composition, when the total weight of the composition is 100% by weight, is preferably 90% by weight or more, more preferably 92% by weight or more, and even more preferably 95% by weight or more, from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material, and is preferably 99.9% by weight or less, from the viewpoint of increasing the concentrations of the p-type semiconductor material and the n-type semiconductor material in the coating liquid and facilitating the formation of a layer of a certain thickness or more.

[0228] The composition may further contain an optional third solvent in addition to the first solvent and the optional second solvent. When the total weight of all the solvents contained in the coating liquid is 100% by weight, the content of the optional third solvent is preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 1% by weight or less. As the optional third solvent, a solvent having a boiling point higher than that of the second solvent is preferable.

[0229] 1.5. Optional Ingredients The composition according to the present embodiment may contain, in addition to the p-type semiconductor material, n-type semiconductor material, insulating material, and solvent, any optional components to the extent that the object and effect of the present invention are not impaired. Examples of the optional components include an ultraviolet absorber, an antioxidant, a sensitizer for enhancing the function of generating charges by absorbed light, and a light stabilizer for enhancing stability against ultraviolet light. The total content of optional components in the composition is preferably 10% by weight or less, more preferably 5% by weight or less, and usually 0% by weight or more.

[0230] [1.6. Content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material] (Concentration of p-type and n-type semiconductor materials in the composition) The total concentration of the p-type semiconductor material and the n-type semiconductor material in the composition can be any suitable concentration according to the required thickness of the active layer.The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less, more preferably 0.01% by weight or more to 20% by weight or less, more preferably 0.01% by weight or more to 10% by weight or less, more preferably 0.01% by weight or more to 5% by weight or less, particularly preferably 0.1% by weight or more to 5% by weight or less.

[0231] (Weight ratio of p-type semiconductor material to n-type semiconductor material (p / n ratio)) The weight ratio of the p-type semiconductor material to the n-type semiconductor material in the composition (p-type semiconductor material / n-type semiconductor material) is preferably 1 / 9 or more, more preferably 1 / 5 or more, even more preferably 1 / 3 or more, and is preferably 9 / 1 or less, more preferably 5 / 1 or less, even more preferably 3 / 1 or less.

[0232] (Total content of p-type semiconductor material, n-type semiconductor material, and insulating material) The total content ratio of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition can be appropriately set depending on, for example, the type of coating method, the viscosity of the components used, etc. The total content ratio of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition is not particularly limited as long as they can be dissolved in the composition, but is preferably 1 wt% or more, more preferably 2 wt% or more, even more preferably 3 wt% or more, and is preferably 20 wt% or less, more preferably 10 wt% or less, even more preferably 7 wt% or less.

[0233] [1.7. Method for producing the composition] The composition can be produced by a conventionally known method. For example, when the first and second solvents are used as the solvent, the composition can be produced by a method of mixing the first and second solvents to prepare a mixed solvent, and adding a p-type semiconductor material, an n-type semiconductor material, and an insulating material to the mixed solvent, or a method of adding a p-type semiconductor material and an insulating material to the first solvent, adding an n-type semiconductor material to the second solvent, and then mixing the first and second solvents to which each material has been added.

[0234] The solvent, the p-type semiconductor material, the n-type semiconductor material, and the insulating material may be mixed by heating to a temperature equal to or lower than the boiling point of the solvent.

[0235] After mixing the solvent with the p-type semiconductor material, the n-type semiconductor material, and the insulating material, the mixture is filtered using a filter, and the filtrate obtained may be used as the composition. As the filter, for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.

[0236] [1.8. Use of the composition] The composition can be suitably used as an ink for forming a film containing a p-type semiconductor material, an n-type semiconductor material, and an insulating material by a coating method. In this specification, "ink" means a liquid material used in the coating method, and is not limited to a colored liquid. In addition, "coating method" includes a method for forming a film (layer) using a liquid material, and examples thereof include slot die coating method, slit coating method, knife coating method, spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, gravure printing method, flexographic printing method, offset printing method, inkjet coating method, dispenser printing method, nozzle coating method, and capillary coating method.

[0237] [2. Membrane] A film according to an embodiment of the present invention includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Hereinafter, the film including the polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material is also referred to as "film A". Examples and preferred examples of the polymer (1) as a p-type semiconductor material, examples and preferred examples of an n-type semiconductor material, and examples and preferred examples of an insulating material are the same as those described in the section [1. Composition].

[0238] The preferred range of the weight ratio of the p-type semiconductor material to the n-type semiconductor material (p-type semiconductor material / n-type semiconductor material) in the film according to this embodiment can be the same as the preferred range of this weight ratio in the composition.

[0239] The preferred range of the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the film according to this embodiment can be the same as the preferred range of this weight ratio in the composition.

[0240] The thickness of the film according to this embodiment can be appropriately set according to the intended function of the film. The thickness of the film according to this embodiment is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more, and is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less.

[0241] The membrane according to the present embodiment may be produced by any method. For example, the membrane according to the present embodiment may be produced by a method including the following steps.

[0242] Step (1): A step of applying the composition to an object to form a coating film. Step (2): A step of drying the coating film. The steps (1) and (2) are usually carried out in this order.

[0243] (Process (1)) The composition contains the polymer (1) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent. The preferred compositions already exemplified can be used as the composition.

[0244] When the film according to this embodiment is used as an active layer of a photoelectric conversion element, examples of the target to which the composition is applied include an electrode, an electron transport layer, and a hole transport layer.

[0245] Any coating method can be used as a method for coating the composition on the coating target. Examples of the method for coating the composition on the coating target in step (1) include the coating methods exemplified above, and among them, spin coating is preferred because it is easy to obtain a coating film with a uniform thickness.

[0246] (Process (2)) The coating film is dried to remove the solvent contained therein. Examples of the method for drying the coating film include a method of directly heating the coating film using a hot plate under an inert gas atmosphere such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, a reduced pressure drying method, and combinations of these methods. Drying conditions such as drying temperature and drying time can be set to any suitable conditions taking into consideration the boiling point of the solvent contained in the composition, the thickness of the coating film, and the like.

[0247] The method for producing a membrane according to this embodiment may include any optional step in addition to the steps (1) and (2).

[0248] [3. Photoelectric conversion element] [3.1. Photoelectric conversion element configuration] The photoelectric conversion element according to one embodiment of the present invention includes a first electrode, the film A, and a second electrode in this order. In the photoelectric conversion element, the film A usually functions as an active layer. When the photoelectric conversion element is irradiated with light, the first electrode is an electrode that outputs positive charges to an external circuit, and the second electrode is an electrode into which positive charges flow from the external circuit. Hereinafter, the photoelectric conversion element of this embodiment will be described with reference to the drawings.

[0249] FIG. 1 is a diagram illustrating a schematic configuration example of a photoelectric conversion element.

[0250] 1, a photoelectric conversion element 10 is provided on a support substrate 11. The photoelectric conversion element 10 includes a first electrode 12 provided so as to be in contact with the support substrate 11, a hole transport layer 13 provided so as to be in contact with the first electrode 12, an active layer 14 provided so as to be in contact with the hole transport layer 13, an electron transport layer 15 provided so as to be in contact with the active layer 14, and a second electrode 16 provided so as to be in contact with the electron transport layer 15. In this configuration example, a sealing member 17 is further provided so as to be in contact with the second electrode 16. Hereinafter, components that can be included in the photoelectric conversion element of this embodiment will be specifically described.

[0251] (substrate) A photoelectric conversion element is usually formed on a substrate (support substrate). In some cases, the element is further sealed by a substrate (sealing substrate). Usually, one of a pair of electrodes consisting of a first electrode and a second electrode is formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that is not chemically changed when a layer containing an organic compound is formed.

[0252] Examples of the material of the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the opposite side to the electrode provided on the opaque substrate side (in other words, the electrode on the side farther from the opaque substrate) is a transparent or semi-transparent electrode.

[0253] (electrode) The photoelectric conversion element includes a pair of electrodes, that is, a first electrode and a second electrode. At least one of the first electrode and the second electrode is preferably a transparent or semi-transparent electrode to allow light to enter.

[0254] Examples of materials for the transparent or semitransparent electrode include conductive metal oxide films and semitransparent metal thin films. Specific examples include conductive materials such as indium oxide, zinc oxide, tin oxide, and their composites, such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, as well as gold, platinum, silver, and copper. Preferred materials for the transparent or semitransparent electrode are ITO, IZO, and tin oxide. Also, transparent conductive films using organic compounds such as polyaniline and its derivatives, and polythiophene and its derivatives as materials may be used as the electrode. The transparent or semitransparent electrode may be either the first electrode or the second electrode.

[0255] If one of the pair of electrodes is transparent or semi-transparent, the other electrode may be an electrode with low light transmittance. Examples of the material of the electrode with low light transmittance include metals and conductive polymers. Specific examples of the material of the electrode 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 metals, or alloys of one or more of these metals with one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, graphite, graphite intercalation compounds, polyaniline and its derivatives, and polythiophene and its derivatives. The alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

[0256] (active layer) The photoelectric conversion element of this embodiment has the film A as an active layer. The active layer, which is the film A according to this embodiment, has a bulk heterojunction type structure and includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Examples and preferred examples of the polymer (1) as a p-type semiconductor material, examples and preferred examples of the n-type semiconductor material, and examples and preferred examples of the insulating material are the same as those described in the section [1. Composition].

[0257] The preferred range of the weight ratio of the p-type semiconductor material to the n-type semiconductor material (p-type semiconductor material / n-type semiconductor material) in the active layer can be the same as the preferred range of said weight ratio in the composition.

[0258] The preferred range of the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the active layer can be the same as the preferred range of said weight ratio in the composition.

[0259] In this embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness considering the balance between suppressing dark current and taking out the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more, particularly from the viewpoint of further reducing dark current. In addition, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less.

[0260] (Middle class) As shown in FIG. 1, the photoelectric conversion element of this embodiment preferably includes an intermediate layer (buffer layer) such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer) as a component for improving characteristics such as photoelectric conversion efficiency.

[0261] Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and a mixture of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonate)) (PEDOT:PSS).

[0262] In one embodiment, the photoelectric conversion element preferably includes a hole transport layer between the first electrode and the active layer, as shown in Figure 1. The hole transport layer has a function of transporting holes from the active layer to the electrode. In another embodiment, the photoelectric conversion element does not need to include a hole transport layer.

[0263] The hole transport layer provided in contact with the first electrode may be particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the first electrode has a function of promoting the injection of holes into the first electrode. The hole transport layer (hole injection layer) may be in contact with the active layer.

[0264] The hole transport layer includes a hole transport material, such as polythiophene and its derivatives, aromatic amine compounds, polymer compounds including structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO3), and molybdenum oxide (MoO3).

[0265] The intermediate layer can be formed by any suitable conventional method, such as a vacuum deposition method or a coating method similar to the method for forming the active layer.

[0266] The photoelectric conversion element according to this embodiment preferably has a configuration in which the intermediate layer is a hole transport layer and an electron transport layer, and the substrate (support substrate), the first electrode, the hole transport layer, the active layer, the electron transport layer, and the second electrode are laminated in this order so as to be in contact with each other.

[0267] As shown in Fig. 1, the photoelectric conversion element of this embodiment preferably includes an electron transport layer as an intermediate layer between the second electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the second electrode. The electron transport layer may be in contact with the second electrode. The electron transport layer may be in contact with the active layer.

[0268] The electron transport layer provided in contact with the second electrode may be particularly called an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the second electrode has a function of promoting the injection of electrons generated in the active layer to the second electrode.

[0269] The electron transport layer contains an electron transporting material, such as polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

[0270] Examples of polyalkyleneimine and its derivatives include polymers obtained by polymerizing one or more alkyleneimines having 2 to 8 carbon atoms, particularly alkyleneimines having 2 to 4 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, by a conventional method, and polymers obtained by reacting them with various compounds to chemically modify them. As polyalkyleneimine and its derivatives, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferred.

[0271] Examples of polymer compounds containing a fluorene structure include poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9,9'-dioctylfluorene)] (PFN) and PFN-P2.

[0272] Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and among them, zinc oxide is preferable.

[0273] Other examples of electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0274] (Sealing member) The photoelectric conversion element of this embodiment preferably further includes a sealing member and is sealed with the sealing member to form a sealed body. The sealing member may be any suitable conventional member known in the art, and may be, for example, a combination of a glass substrate (sealing substrate) and a sealing material (adhesive) such as a UV-curable resin.

[0275] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0276] The sealing layer is preferably formed from 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 sealing layer include organic materials such as trifluoropolyethylene, polytrifluorochloroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

[0277] The sealing member is generally made of a material that can withstand a heat treatment that may be performed when the photoelectric conversion element is applied, for example, when the element is incorporated into a device of the application example described below.

[0278] [3.2. Method for manufacturing photoelectric conversion element] The photoelectric conversion element of the present embodiment can be manufactured by any method, for example, by combining a suitable forming method with the materials selected for forming the components.

[0279] Hereinafter, as an embodiment of the present invention, a method for manufacturing a photoelectric conversion element having a configuration in which a substrate (support substrate), a first electrode, a hole transport layer, a film A as an active layer, an electron transport layer, and a second electrode are in contact with each other in this order will be described.

[0280] (Process of preparing the substrate) In this step, for example, a support substrate provided with a first electrode is prepared. Alternatively, a substrate provided with a conductive thin film formed from the electrode material already described may be purchased from the market, and the conductive thin film may be patterned to form the first electrode as necessary, thereby preparing a support substrate provided with the first electrode.

[0281] In the method for producing a photoelectric conversion element according to the present embodiment, the method for forming the first electrode on the supporting substrate is not particularly limited. The first electrode can be formed on the structure on which the first electrode is to be formed (e.g., supporting substrate, active layer, hole transport layer) by any suitable conventional method such as vacuum deposition, sputtering, ion plating, plating, or coating using the material already described.

[0282] (Hole transport layer forming process) 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.

[0283] The method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process for forming the hole transport layer, it is preferable to form the hole transport layer by any suitable coating method known in the art. The hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material and solvent of the hole transport layer already described or a vacuum deposition method.

[0284] (Active layer formation process) In the method for producing a photoelectric conversion element according to the present embodiment, a film A is formed as an active layer on a hole transport layer. The film A can be formed by any suitable conventionally known formation process. In the present embodiment, the film A as an active layer can be produced by a coating method using the composition.

[0285] The film A as the active layer can be formed by the same method as the film manufacturing method described in [2. Film]. In this embodiment, the film A as the active layer can be formed by a process including a step of applying the composition containing the polymer (1) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent onto a hole transport layer to form a coating film, and then a step of drying the coating film.

[0286] (Electron transport layer formation process) The method for manufacturing a photoelectric conversion element of this embodiment includes a step of forming an electron transport layer (electron injection layer) provided on an active layer.

[0287] The method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process for forming the electron transport layer, it is preferable to form the electron transport layer by any suitable conventional vacuum deposition method.

[0288] (Step of forming second electrode) The method for forming the second electrode is not particularly limited. The second electrode can be formed on the electron transport layer by any suitable method known in the art, such as coating, vacuum deposition, sputtering, ion plating, or plating, using the above-mentioned electrode material. The photoelectric conversion element of this embodiment is manufactured by the above steps.

[0289] (Sealing Body Forming Process) In forming the sealed body, in this embodiment, any suitable sealing material (adhesive) and substrate (sealing substrate) known in the art are used. Specifically, a sealing material such as a UV-curable resin is applied onto a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the support substrate and sealing substrate are bonded together without any gaps by the sealing material. Then, the photoelectric conversion element is sealed in the gap between the support substrate and the sealing substrate by a method such as UV light irradiation suitable for the selected sealing material, thereby obtaining a sealed body of the photoelectric conversion element.

[0290] [3.3. Uses of photoelectric conversion elements] The photoelectric conversion element of this embodiment can be used in applications such as a photodetector element and a solar cell. More specifically, the photoelectric conversion element of this embodiment can generate a photocurrent by irradiating light from the transparent or semitransparent electrode side with a voltage (reverse bias voltage) applied between the electrodes, and can be operated as a photodetection element (photosensor). In addition, a plurality of photodetection elements can be integrated to be used as an image sensor. Thus, the photoelectric conversion element of this embodiment can be particularly suitably used as a photodetection element.

[0291] In addition, the photoelectric conversion element of the present embodiment can generate photovoltaic power between the electrodes when irradiated with light, and can operate as a solar cell. A solar cell module can also be formed by integrating a plurality of photoelectric conversion elements.

[0292] (Application example of photoelectric conversion element) The photoelectric conversion element according to this embodiment can be suitably applied as a photodetector element to detection units provided in various electronic devices such as workstations, personal computers, portable information terminals, entrance and exit management systems, digital cameras, and medical equipment.

[0293] The photoelectric conversion element of this embodiment can be suitably applied to the image detection units (e.g., image sensors such as X-ray sensors) for solid-state imaging devices such as X-ray imaging devices and CMOS image sensors, detection units (e.g., near-infrared sensors) of biometric information authentication devices that detect predetermined characteristics of a part of a living body, such as fingerprint detection units, face detection units, vein detection units and iris detection units, and detection units of optical biosensors such as pulse oximeters, which are provided in the above-mentioned exemplary electronic devices.

[0294] The photoelectric conversion element of this embodiment can be suitably applied as an image detection section for a solid-state imaging device, and further to a time-of-flight (TOF) type distance measurement device.

[0295] In TOF distance measuring devices, the distance is measured by receiving the light reflected by the object to be measured using a photoelectric conversion element. Specifically, the distance to the object to be measured is calculated by detecting the flight time of the light emitted from the light source, which is reflected by the object to be measured and returns as reflected light. There are two types of TOF: direct TOF and indirect TOF. In the direct TOF method, the difference between the time when the light is emitted from the light source and the time when the reflected light is received by the photoelectric conversion element is directly measured, while in the indirect TOF method, the change in the amount of charge accumulation that depends on the flight time is converted into a time change to measure the distance. The distance measuring principle used in the indirect TOF method to obtain the flight time by charge accumulation includes the continuous wave (especially sinusoidal wave) modulation method, which obtains the flight time from the phase of the light emitted from the light source and the reflected light reflected by the object to be measured, and the pulse modulation method.

[0296] Below, examples of configurations of detection units to which the photoelectric conversion element of this embodiment can be suitably applied will be described with reference to the drawings, including an image detection unit for a solid-state imaging device and an image detection unit for an X-ray imaging device, a fingerprint detection unit and a vein detection unit for a biometric authentication device (e.g., a fingerprint authentication device or a vein authentication device), and an image detection unit for a TOF type distance measuring device (indirect TOF method).

[0297] (Image detector for solid-state imaging device) FIG. 2 is a diagram illustrating a schematic configuration example of an image detection unit for a solid-state imaging device.

[0298] The image detection unit 1 includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20, a photoelectric conversion element 10 according to an embodiment of the present invention provided on the interlayer insulating film 30, an interlayer wiring portion 32 provided to penetrate the interlayer insulating film 30 and electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10, a sealing layer 40 provided to cover the photoelectric conversion element 10, and a color filter 50 provided on the sealing layer 40.

[0299] The CMOS transistor substrate 20 has any suitable conventionally known configuration in a manner according to the design.

[0300] The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and is equipped with functional elements such as CMOS transistor circuits (MOS transistor circuits) for implementing various functions.

[0301] Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.

[0302] A signal readout circuit and the like are formed on the CMOS transistor substrate 20 using such functional elements and wiring.

[0303] The interlayer insulating film 30 can be made of any suitable insulating material known in the art, such as silicon oxide, insulating resin, etc. The interlayer wiring portion 32 can be made of any suitable conductive material known in the art (wiring material), such as copper, tungsten, etc. The interlayer wiring portion 32 can be, for example, a hole wiring formed simultaneously with the formation of a wiring layer, or a buried plug formed separately from the wiring layer.

[0304] The sealing layer 40 can be made of any suitable material known in the art, provided that it can prevent or suppress the penetration of harmful substances such as oxygen and water that may cause functional deterioration of the photoelectric conversion element 10. The sealing layer 40 can have a structure similar to that of the sealing member 17 already described.

[0305] The color filter 50 may be, for example, a primary color filter made of any suitable material known in the art and adapted to the design of the image detection unit 1. Also, the color filter 50 may be a complementary color filter that can be made thinner than the primary color filter. The complementary color filter may be, for example, a combination of three types of color filters: (yellow, cyan, magenta), three types of color filters: (yellow, cyan, transparent), three types of color filters: (yellow, transparent, magenta), and three types of color filters: (transparent, cyan, magenta). These may be arranged in any suitable manner adapted to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.

[0306] The light received by the photoelectric conversion element 10 through the color filter 50 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of light received, and is output to the outside of the photoelectric conversion element 10 via the electrode as a received light signal, i.e., an electrical signal corresponding to the object to be imaged.

[0307] Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring section 32, read out by a signal readout circuit built into the CMOS transistor substrate 20, and subjected to signal processing by any suitable conventionally known functional section not shown in the figure, thereby generating image information based on the imaging target.

[0308] (Fingerprint detection section) FIG. 3 is a diagram illustrating a configuration example of a fingerprint detection unit that is integrally configured with the display device.

[0309] The display device 2 of the mobile information terminal includes a fingerprint detection unit 100 having a photoelectric conversion element 10 according to an embodiment of the present invention as its main component, and a display panel unit 200 provided on the fingerprint detection unit 100 and displaying a predetermined image.

[0310] In this configuration example, the fingerprint detection section 100 is provided in an area that coincides with the display area 200a of the display panel section 200. In other words, the display panel section 200 is laminated above the fingerprint detection section 100 as one unit.

[0311] When fingerprint detection is performed only in a portion of the display area 200a, the fingerprint detection unit 100 may be provided so as to correspond to only that portion of the display area 200a.

[0312] The fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The fingerprint detection unit 100 may include any suitable conventionally known members such as a protection film, a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film, which are not shown, in a form corresponding to a design that obtains desired characteristics. The fingerprint detection unit 100 may also adopt the configuration of the image detection unit already described.

[0313] The photoelectric conversion elements 10 may be included in the display region 200a in any manner. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

[0314] As already described, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrodes or second electrodes) in a matrix pattern, for example.

[0315] The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal according to the amount of light received, and is output via the electrodes to the outside of the photoelectric conversion element 10 as a received light signal, i.e., an electrical signal corresponding to the captured fingerprint.

[0316] In this configuration example, the display panel unit 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel. The display panel unit 200 may be configured with any suitable display panel having a conventionally known configuration, such as a liquid crystal display panel including a light source such as a backlight, instead of an organic EL display panel.

[0317] The display panel unit 200 is provided on the fingerprint detection unit 100 already described. The display panel unit 200 includes an organic electroluminescence element (organic EL element) 220 as a functional unit that performs an essential function. The display panel unit 200 may further include any suitable conventionally known member such as a substrate (support substrate 210 or sealing substrate 240) such as a glass substrate, a sealing member, a barrier film, a polarizing plate such as a circular polarizing plate, and a touch sensor panel 230 in a mode corresponding to desired characteristics.

[0318] In the configuration example described above, the organic EL element 220 is used as a light source for the pixels in the display area 200a, and is also used as a light source for capturing an image of a fingerprint in the fingerprint detection unit 100.

[0319] Here, the operation of the fingerprint detection unit 100 will be briefly described. When fingerprint authentication is performed, the fingerprint detection unit 100 detects a fingerprint using light emitted from the organic EL element 220 of the display panel unit 200. Specifically, the light emitted from the organic EL element 220 passes through components present between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is reflected by the skin (finger surface) of the fingertip of a finger placed in contact with the surface of the display panel unit 200 within the display area 200a. At least a part of the light reflected by the finger surface passes through components present therebetween and is received by the photoelectric conversion element 10, and is converted into an electrical signal according to the amount of light received by the photoelectric conversion element 10. Then, image information about the fingerprint on the finger surface is composed from the converted electrical signal.

[0320] The portable information terminal equipped with the display device 2 performs fingerprint authentication by comparing the obtained image information with pre-recorded fingerprint data for fingerprint authentication through any suitable step known in the art.

[0321] (Image detector for X-ray imaging device) FIG. 4 is a diagram illustrating a schematic configuration example of an image detection unit for an X-ray imaging device.

[0322] The image detection unit 1 for an X-ray imaging device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20, a photoelectric conversion element 10 according to an embodiment of the present invention provided on the interlayer insulating film 30, an interlayer wiring portion 32 provided to penetrate the interlayer insulating film 30 and electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10, a sealing layer 40 provided to cover the photoelectric conversion element 10, a scintillator 42 provided on the sealing layer 40, a reflective layer 44 provided to cover the scintillator 42, and a protective layer 46 provided to cover the reflective layer 44.

[0323] The CMOS transistor substrate 20 has any suitable conventionally known configuration in a manner according to the design.

[0324] The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and is equipped with functional elements such as CMOS transistor circuits (MOS transistor circuits) for implementing various functions.

[0325] Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.

[0326] A signal readout circuit and the like are formed on the CMOS transistor substrate 20 using such functional elements and wiring.

[0327] The interlayer insulating film 30 can be made of any suitable insulating material known in the art, such as silicon oxide, insulating resin, etc. The interlayer wiring portion 32 can be made of any suitable conductive material known in the art (wiring material), such as copper, tungsten, etc. The interlayer wiring portion 32 can be, for example, a hole wiring formed simultaneously with the formation of a wiring layer, or a buried plug formed separately from the wiring layer.

[0328] The sealing layer 40 can be made of any suitable material known in the art, provided that it can prevent or suppress the penetration of harmful substances such as oxygen and water that may cause functional deterioration of the photoelectric conversion element 10. The sealing layer 40 can have a structure similar to that of the sealing member 17 already described.

[0329] The scintillator 42 can be made of any suitable conventional material that is known in accordance with the design of the image detection unit 1 for the X-ray imaging device. Suitable examples of materials for the scintillator 42 include inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadolinium oxysulfide), and GSO (gadolinium silicate), organic crystals of organic materials such as anthracene, naphthalene, and stilbene, organic liquids in which organic materials such as diphenyloxazole (PPO) and terphenyl (TP) are dissolved in organic solvents such as toluene, xylene, and dioxane, gases such as xenon and helium, and plastics.

[0330] The above components can be arranged in any suitable manner corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that the scintillator 42 can convert the incident X-rays into light having a wavelength centered in the visible range and generate image data.

[0331] The reflective layer 44 reflects the light converted by the scintillator 42. The reflective layer 44 can reduce the loss of the converted light and increase the detection sensitivity. The reflective layer 44 can also block light that is directly incident from the outside.

[0332] The protective layer 46 can be made of any suitable material known in the art, provided that it can prevent or suppress the penetration of harmful substances such as oxygen and water that may cause the functionality of the scintillator 42 to deteriorate.

[0333] Here, the operation of the image detection unit 1 for the X-ray imaging device having the above configuration will be briefly described.

[0334] When radiation energy such as X-rays or gamma rays is incident on the scintillator 42, the scintillator 42 absorbs the radiation energy and converts it into light (fluorescence) with wavelengths in the ultraviolet to infrared range centered on the visible range. The light converted by the scintillator 42 is then received by the photoelectric conversion element 10.

[0335] In this way, the light received by the photoelectric conversion element 10 via the scintillator 42 is converted by the photoelectric conversion element 10 into an electrical signal according to the amount of received light, and is output via the electrodes to the outside of the photoelectric conversion element 10 as a received light signal, i.e., an electrical signal corresponding to the imaging target. The radiation energy (X-rays) to be detected may be incident from either the scintillator 42 side or the photoelectric conversion element 10 side.

[0336] Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring section 32, read out by a signal readout circuit built into the CMOS transistor substrate 20, and subjected to signal processing by any suitable conventionally known functional section not shown in the figure, thereby generating image information based on the imaging target.

[0337] (Vein detection section) FIG. 5 is a diagram illustrating a configuration example of a vein detection unit for use in a vein authentication device. The vein detection unit 300 for the vein authentication device is composed of a cover unit 306 that defines an insertion unit 310 into which a finger to be measured (e.g., the fingertip of one or more fingers, the finger and the palm) is inserted during measurement, a light source unit 304 that is provided in the cover unit 306 and irradiates light onto the measurement object, a photoelectric conversion element 10 that receives the light irradiated from the light source unit 304 through the measurement object, a support substrate 11 that supports the photoelectric conversion element 10, and a glass substrate 302 that is disposed to face each other across the support substrate 11 and the photoelectric conversion element 10, is spaced a predetermined distance from the cover unit 306, and defines the insertion unit 306 together with the cover unit 306.

[0338] In this configuration example, the light source unit 304 is configured integrally with the cover unit 306 so as to sandwich and separate the photoelectric conversion element 10 from the object to be measured during use, but the light source unit 304 does not necessarily have to be positioned on the cover unit 306 side.

[0339] Provided that the light from the light source unit 304 can be efficiently irradiated onto the measurement object, for example, a reflection type imaging method in which the measurement object is irradiated from the photoelectric conversion element 10 side may be used.

[0340] The vein detection unit 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The vein detection unit 300 may include any suitable conventionally known members such as a protection film, a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light blocking film, and a finger placement guide, all of which are not shown, in a form corresponding to a design that obtains desired characteristics. The vein detection unit 300 may also employ the configuration of the image detection unit 1 already described.

[0341] The photoelectric conversion element 10 may be included in any manner. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

[0342] As already described, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrodes or second electrodes) in a matrix pattern, for example.

[0343] The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal according to the amount of received light, and is output to the outside of the photoelectric conversion element 10 via the electrodes as a received light signal, i.e., an electrical signal corresponding to the imaged vein.

[0344] During vein detection (during use), the measurement target may or may not be in contact with glass substrate 302 on the photoelectric conversion element 10 side.

[0345] Here, the operation of the vein detection unit 300 will be briefly described. During vein detection, the vein detection unit 300 detects the vein pattern of the measurement object using light emitted from the light source unit 304. Specifically, the light emitted from the light source unit 304 passes through the measurement object and is converted into an electrical signal according to the amount of light received by the photoelectric conversion element 10. Then, image information of the vein pattern of the measurement object is composed from the converted electrical signal.

[0346] In the vein authentication device, vein authentication is performed by comparing the obtained image information with pre-recorded vein data for vein authentication through any suitable step known in the art.

[0347] (Image detector for TOF distance measuring device) FIG. 6 is a diagram showing a schematic configuration example of an image detection unit for an indirect type TOF distance measuring device.

[0348] The image detection unit 400 for a TOF type distance measuring device includes a CMOS transistor substrate 20, an interlayer insulating film 30 arranged to cover the CMOS transistor substrate 20, a photoelectric conversion element 10 according to an embodiment of the present invention arranged on the interlayer insulating film 30, two floating diffusion layers 402 arranged at a distance to sandwich the photoelectric conversion element 10, an insulating layer 40 arranged to cover the photoelectric conversion element 10 and the floating diffusion layer 402, and two photogates 404 arranged on the insulating layer 40 and arranged at a distance from each other.

[0349] A part of the insulating layer 40 is exposed from the gap between the two spaced apart photogates 404, and the remaining area is shielded from light by a light shielding portion 406. The CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected by an interlayer wiring portion 32 provided to penetrate the interlayer insulating film 30.

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

[0351] In this configuration example, the insulating layer 40 may be of any suitable conventionally known configuration, such as a field oxide film made of silicon oxide.

[0352] Photogate 404 may be constructed from any suitable material known in the art, such as polysilicon.

[0353] The image detection unit 400 for the TOF type distance measuring device includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The image detection unit 400 for the TOF type distance measuring device may include any suitable conventionally known members such as a protection film, a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film, which are not shown, in a form corresponding to a design that obtains desired characteristics.

[0354] Here, the operation of the image detection unit 400 for the TOF type distance measuring device will be briefly described.

[0355] Light is emitted from a light source, reflected from the object to be measured, and the reflected light is received by the photoelectric conversion element 10. Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402, and by applying pulses alternately, the signal charge generated by the photoelectric conversion element 10 is transferred to one of the two floating diffusion layers 402, and the charge is accumulated in the floating diffusion layer 402. If the light pulse arrives so as to span equally with respect to the timing at which the two photogates 404 are opened, the amount of charge accumulated in the two floating diffusion layers 402 will be equal. If the light pulse arrives at one photogate 404 with a delay from the timing at which the light pulse arrives at the other photogate 404, a difference occurs in the amount of charge accumulated in the two floating diffusion layers 402.

[0356] The difference in the amount of charge accumulated in the floating diffusion layers 402 depends on the delay time of the optical pulse. The distance L to the measurement target is expressed as L=(1 / 2)ctd using the round-trip time td of light and the speed of light c. Therefore, if the delay time can be estimated from the difference in the amount of charge in the two floating diffusion layers 402, the distance to the measurement target can be calculated.

[0357] The amount of light received by the photoelectric conversion element 10 is converted into an electrical signal as the difference between the amounts of charge accumulated in the two floating diffusion layers 402, and is output to the outside of the photoelectric conversion element 10 as a received light signal, i.e., an electrical signal corresponding to the object to be measured.

[0358] Next, the received light signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring section 32, read out by a signal readout circuit built into the CMOS transistor substrate 20, and subjected to signal processing by any suitable conventionally known functional section not shown in the figure, thereby generating distance information based on the object to be measured.

[0359] [4. Photodetector] As described above, the organic photoelectric conversion element of the present embodiment can have a light detection function of converting irradiated light into an electrical signal according to the amount of received light and outputting it to an external circuit via the electrodes. Therefore, the photodetector according to one embodiment of the present invention can have a photodetection function by including the organic photoelectric conversion element. The photodetector according to this embodiment may be the organic photoelectric conversion element itself, or may include a functional element for voltage control in addition to the organic photoelectric conversion element. EXAMPLES

[0360] Examples are given below to explain the present invention in more detail. The present invention is not limited to the examples described below. The following examples were carried out under normal temperature and pressure conditions unless otherwise specified. In addition, "%" and "parts" represent "% by weight" and "parts by weight", respectively, unless otherwise specified.

[0361] <Materials used> The p-type semiconductor material (electron donor compound), n-type semiconductor material (electron acceptor compound), and insulating material (compound not involved in the photoelectric conversion process) used in the following examples are as follows.

[0362] (p-type semiconductor material) As the p-type semiconductor material, the following polymers P-1 to P-4, which are high molecular weight compounds, were used.

[0363] [ka]

[0364] The polymer compound (polymer) P-1, which is a p-type semiconductor material, was synthesized with reference to the method described in WO 2013 / 051676 and used. The polymer compound (polymer) P-2, which is a p-type semiconductor material, was synthesized with reference to the method described in WO 2011 / 052709 and used. As the polymer compound (polymer) P-3, which is a p-type semiconductor material, PDTSTPD (trade name, manufactured by 1-material Co., Ltd.) was purchased from the market and used. As the polymer compound (polymer) P-4, which is a p-type semiconductor material, PBDTTPD (trade name, manufactured by 1-material Co., Ltd.) was purchased from the market and used.

[0365] (n-type semiconductor material) As the n-type semiconductor material, the following compounds N-1 to N-2 were used.

[0366] [ka]

[0367] The compound N-1, which is an n-type semiconductor material, was obtained commercially as Coi8DFIC (product name, manufactured by 1-material Co., Ltd.). As the n-type semiconductor material, compound N-2, E100 (trade name, manufactured by Frontier Carbon Co., Ltd.) was purchased from the market and used.

[0368] (Insulating materials) As the insulating material, the following polymers Z-1 to Z-2 were used.

[0369] [ka]

[0370] The insulating material, compound Z-1, was obtained commercially and used as Polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (weight average molecular weight Mw 118,000 or less, manufactured by Aldrich). The insulating material, compound Z-2, was obtained commercially and used as Polystyrene-block-polyisoprene-block-polystyrene (number average molecular weight Mn 1900, manufactured by Aldrich).

[0371] [Solubility of insulating materials in solvents] The solubility of the insulating material in a solvent was evaluated as follows. A mixed solvent was prepared by using tetralin as the first solvent and butyl benzoate as the second solvent, with the weight ratio of the first solvent to the second solvent being 97:3. 1 part by weight of compound Z-1 or Z-2, which is an insulating material, was added to 99 parts by weight of the mixed solvent, and stirred at 60° C. for 1 hour. After cooling to 25° C., the mixture after stirring was visually observed to confirm whether any insulating material remained dissolved. When no insulating material remained dissolved, the solubility in the mixed solvent was determined to be “good.” The solubility in tetralin was also evaluated in the same manner as in the evaluation of the solubility in the mixed solvent, except that the mixed solvent was changed to a single solvent of tetralin. The evaluation results are shown in the table below. It was found that insulating materials Z-1 and Z-2 were materials that dissolved in the mixed solvent or tetralin at 25° C. to a concentration of 0.1% by weight or more.

[0372] [Table 1]

[0373] An ink composition was prepared using compound Z-1 or Z-2 as the insulating material.

[0374] [Preparation of ink (composition)] [Preparation Example 1] Preparation of Ink I-1 A mixed solvent was prepared by using tetralin as the first solvent and butyl benzoate as the second solvent, with the weight ratio of the first solvent to the second solvent being 97:3.

[0375] To the resulting mixed solvent, a polymer compound (polymer) P-1, which is a p-type semiconductor material, was added at a concentration of 1 wt% relative to the total weight of the ink, a compound N-1, which is an n-type semiconductor material, was added at a concentration of 1 wt% relative to the total weight of the ink, and a compound Z-1, which is an insulating material, was added at a concentration of 0.5 wt% relative to the total weight of the ink, and the mixture was stirred at 60°C for 8 hours to obtain a mixed liquid. The resulting mixed liquid was filtered using a filter to obtain ink I-1.

[0376] [Preparation Example 2] Preparation of Ink I-2 Tetralin solvent was used instead of the mixed solvent. Instead of compound N-1, compound N-2, an n-type semiconductor material, was used, and compound N-2 was added to a tetralin solvent at a concentration of 2% by weight relative to the total weight of the ink. Compound Z-2, an insulating material, was used instead of compound Z-1, and compound Z-2 was added to the tetralin solvent at a concentration of 1% by weight relative to the total weight of the ink. Except for the above, the same procedure as in Preparation Example 1 was repeated to obtain Ink I-2.

[0377] [Preparation Example 3] Preparation of Ink I-3 Tetralin solvent was used instead of the mixed solvent. Instead of polymer P-1, polymer compound (polymer) P-2, which is a p-type semiconductor material, was used. Instead of compound N-1, compound N-2, an n-type semiconductor material, was used, and compound N-2 was added to a tetralin solvent at a concentration of 2% by weight relative to the total weight of the ink. Compound Z-2 was added to a tetralin solvent at a concentration of 1% by weight based on the total weight of the ink. Except for the above, the same procedure as in Preparation Example 1 was repeated to obtain Ink I-3.

[0378] [Comparative Preparation Example 1] Preparation of Ink C-1 Tetralin solvent was used instead of the mixed solvent. Instead of polymer P-1, polymer compound (polymer) P-3, which is a p-type semiconductor material, was used. Instead of compound N-1, compound N-2, an n-type semiconductor material, was used, and compound N-2 was added to a tetralin solvent at a concentration of 2% by weight relative to the total weight of the ink. Compound Z-2 was added to a tetralin solvent at a concentration of 1% by weight based on the total weight of the ink. Except for the above, the same procedure as in Preparation Example 1 was repeated to obtain Ink C-1.

[0379] [Comparative Preparation Example 2] Preparation of Ink C-2 Tetralin solvent was used instead of the mixed solvent. Instead of polymer P-1, polymer compound (polymer) P-4, which is a p-type semiconductor material, was used. Instead of compound N-1, compound N-2, an n-type semiconductor material, was used, and compound N-2 was added to a tetralin solvent at a concentration of 2% by weight relative to the total weight of the ink. Compound Z-2 was added to a tetralin solvent at a concentration of 1% by weight based on the total weight of the ink. Except for the above, the same procedure as in Preparation Example 1 was repeated to obtain Ink C-2.

[0380] The formulations of each preparation example are shown in the table below.

[0381] [Table 2]

[0382] <Production and evaluation of photoelectric conversion elements> [Example 1] (1) Manufacture of photoelectric conversion elements and their encapsulated bodies A photoelectric conversion element and a sealed body thereof were manufactured as follows.

[0383] A glass substrate was prepared on which a thin ITO film (first electrode) with a thickness of 50 nm was formed by sputtering in the form of multiple lines (hereinafter referred to as stripes) arranged parallel to each other and spaced apart. Ozone UV treatment was then performed on this glass substrate as a surface treatment.

[0384] Next, a coating of ink I-1 was formed on the thin ITO film by spin coating, and then the coating was dried by heating for 10 minutes using a hot plate heated to 100°C under a nitrogen gas atmosphere to form an active layer 1. The thickness of the formed active layer was about 500 nm.

[0385] Next, in a resistance heating deposition apparatus, a calcium (Ca) layer was formed to a thickness of about 5 nm on the formed active layer 1 to serve as an electron transport layer. A metal mask was used when forming the Ca layer so that the striped ITO thin film and the Ca layer would intersect.

[0386] Next, a silver (Ag) layer was formed on the formed electron transport layer to a thickness of about 60 nm to form a second electrode. A metal mask was used when forming the Ag layer so that the striped ITO thin film and the Ag layer would intersect. A pixel is the unit of the portion where the ITO thin film, the Ca layer, and the Ag layer overlap when viewed from the thickness direction, and six pixels were formed on one substrate. The effective area of ​​a pixel is the area where the ITO thin film, the Ca layer, and the Ag layer overlap when viewed from the thickness direction.

[0387] Through the above steps, a photoelectric conversion element was manufactured on the glass substrate. The obtained structure was designated as Sample 1.

[0388] Next, a UV-curable sealant was applied as a sealant on a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was attached. Then, UV light was irradiated to seal the photoelectric conversion element in the gap between the support substrate and the sealing substrate. This resulted in a sealed body of the photoelectric conversion element. When the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate was viewed from the thickness direction, the planar shape was a square of 2 mm x 2 mm.

[0389] (2) Evaluation of dark current of photoelectric conversion element In a dark state where no light was irradiated, a voltage of -8V to 2V was applied to the encapsulated photoelectric conversion element produced, and evaluation was performed. The dark current was measured and evaluated using a source meter (KEITHLEY 2450 Source Meter, manufactured by Keithley Instruments). The current value when a voltage of -8V was applied, measured using a known method, was obtained as the dark current value, and the variation in the dark current of 6 pixels in one substrate was evaluated.

[0390] Among the six pixels on one board, if the dark current values ​​of the other five pixels are all within 10 times the lowest dark current value at a voltage of -8V, the degree of variation in dark current is evaluated as "Good." On the other hand, if any of the other five pixels has a dark current value that exceeds 10 times the lowest value, the degree of variation in dark current is evaluated as "Bad."

[0391] The evaluation results of the dark current variation in Example 1 are shown in Table 3.

[0392] [Example 2] (1) Manufacture of photoelectric conversion elements and their encapsulated bodies A photoelectric conversion element and a sealed body thereof were manufactured as follows.

[0393] A glass substrate was prepared on which a thin film of ITO (second electrode) was formed in a stripe shape with a thickness of 50 nm by sputtering, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

[0394] Next, a solution of polyethyleneimine ethoxylate (PEIE) aqueous solution (manufactured by Aldrich, product name polyethyleneimine, 80% ethoxylated solution, weight average molecular weight 110,000) diluted 1000 times with ultrapure water was used as a coating solution for forming an electron transport layer, and was applied by spin coating onto the ITO thin film on the glass substrate that had been subjected to ozone UV treatment to form a coating film. The glass substrate on which the coating film was formed was heated at 100°C for 10 minutes using a hot plate to harden the coating film, thereby forming an electron transport layer on the ITO thin film, which was the second electrode.

[0395] Next, the ink (I-2) was applied onto the thin ITO film by spin coating, and then the film was dried by heating for 10 minutes using a hot plate heated to 100° C. under a nitrogen gas atmosphere to form an active layer 2. The thickness of the formed active layer was about 500 nm.

[0396] Next, in a resistance heating deposition apparatus, molybdenum oxide (MoO3) was deposited to a thickness of about 15 nm on the formed active layer 2 to form a hole transport layer, which was a MoO3 layer. A metal mask was used when forming the MoO3 layer so that the striped ITO thin film and the MoO3 layer would intersect.

[0397] Next, a silver (Ag) layer was formed on the hole transport layer to a thickness of about 60 nm to form a first electrode. A metal mask was used when forming the Ag layer so that the striped ITO thin film and the Ag layer would intersect.

[0398] The unit of overlapping area between the ITO thin film and the MoO3 and Ag layers when viewed from the thickness direction is a pixel, and six pixels were formed on one substrate. The effective area of ​​a pixel is the area where the ITO thin film and the MoO3 and Ag layers overlap when viewed from the thickness direction.

[0399] Through the above steps, a photoelectric conversion element was manufactured on the glass substrate. The obtained structure was designated as Sample 2.

[0400] Next, a UV-curable sealant was applied as a sealant on a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was attached. Then, UV light was irradiated to seal the photoelectric conversion element in the gap between the support substrate and the sealing substrate. This resulted in a sealed body of the photoelectric conversion element. When the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate was viewed from the thickness direction, the planar shape was a square of 2 mm x 2 mm.

[0401] (2) Evaluation of dark current of photoelectric conversion element In the same manner as in Example 1, the variation in dark current was evaluated for six pixels in one substrate. The evaluation results are shown in Table 3.

[0402] [Example 3] Using ink (I-3) instead of ink (I-2), the rotation speed in the spin coating method was adjusted to obtain a film thickness of 500 nm, to obtain active layer 3. Except for this, a sealed body of a photoelectric conversion element was manufactured in the same manner as in Example 2 already described, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.

[0403] [Comparative Examples 1 and 2] Using inks (C-1) and (C-2) instead of ink (I-2), the rotation speed in the spin coating method was adjusted to obtain a film thickness of 500 nm, to obtain active layers 4 and 5, respectively. Except for this, sealed photoelectric conversion elements were manufactured in the same manner as in Example 2 already described, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.

[0404] [Table 3]

[0405] As is clear from Table 3, the elements (samples 1 to 3) of Examples 1 to 3, in which active layers are formed from compositions (inks (I-1) to (I-3)) containing a polymer represented by formula (I) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, have good evaluation results for the variation in dark current. On the other hand, the elements (samples 4 and 5) of Comparative Examples 1 and 2, in which the active layer was formed from a composition (inks (C-1) to (C-2)) that did not contain the polymer represented by formula (I) as the p-type semiconductor material, showed poor evaluation results for the variation in dark current. The inks (C-1) and (C-2) according to Comparative Examples 1 and 2 contain the insulating material Z-2, similar to the inks (I-2) and (I-3) according to Examples 2 and 3. However, since the evaluation results of the dark current variation in Comparative Examples 1 and 2 are poor, it is presumed that some kind of interaction occurs between the polymer represented by formula (I) as the p-type semiconductor material and the insulating material. It is presumed that such an interaction affects the dissolution state of each component, the process of drying the active layer, and the like, and thus affects the film thickness distribution of the active layer. However, the above presumption does not limit the present invention. [Explanation of symbols]

[0406] 1 Image detection section 2 Display device 10 Photoelectric conversion element 11, 210 Support substrate 12 First electrode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Second electrode 17 Sealing member 20 CMOS transistor substrate 30 Interlayer insulating film 32 Interlayer wiring section 40 Sealing layer 42 Scintillator 44 Reflective layer 46 Protective layer 50 Color Filters 100 Fingerprint detection unit 200 Display panel section 200a display area 220 Organic EL element 230 Touch Sensor Panel 240 Sealing substrate 300 Vein detection unit 302 Glass substrate 304 Light source section 306 Cover part 310 Insertion section 400 Image detector for TOF distance measuring device 402 Floating Diffusion Layer 404 Photogate 406 Shading part

Claims

1. A composition comprising a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, The insulating material is a material that dissolves in the solvent at 25° C. in an amount of 0.1% by weight or more, a content of the insulating material in the composition is 0.1% by weight or more and 5% by weight or less, when the total weight of the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent is 100% by weight; The p-type semiconductor material comprises a polymer containing a constitutional unit represented by the following formula (I): 【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 the following formulae (Z-1) to (Z-4). 【Chemistry 2】 (In formulas (Z-1) to (Z-4), R is Hydrogen atoms, Halogen atoms, 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 optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; Cyano group, Nitro group, -C(=O)-R ａ or -SO ２ -R ｂ represents a group represented by R ａ and R ｂ are each independently Hydrogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent. In formulas (Z-1) to (Z-4), the two R's may be the same or different.

2. The composition of claim 1 , wherein the insulating material comprises a polymer containing a constitutional unit represented by the following formula (II): 【Chemistry 3】 (In formula (II), R ｉ１ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms; R ｉ２ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by formula (III-2), or a group represented by formula (III-3). 【Chemistry 4】 (In formula (III-1), Multiple R ｉ２ａ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. 【Chemistry 5】 (In formula (III-2), R ｉ２ｂ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 【Chemistry 6】 (In formula (III-3), R ｉ２ｃ represents an alkyl group having 1 to 20 carbon atoms.

3. A process for applying the composition to an object to be coated to form a coating film; drying the coating; A method for producing a membrane, comprising: The composition, A semiconductor device comprising a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent; The insulating material is a material that dissolves in the solvent at 25° C. in an amount of 0.1% by weight or more, a content of the insulating material in the composition is 0.1% by weight or more and 5% by weight or less, when the total weight of the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent is 100% by weight; The method for producing a film, wherein the p-type semiconductor material comprises a polymer including a constitutional unit represented by the following formula (I): 【Chemistry 7】 (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 the following formulae (Z-1) to (Z-4). 【Chemistry 8】 (In formulas (Z-1) to (Z-4), R is Hydrogen atoms, Halogen atoms, 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 optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; Cyano group, Nitro group, -C(=O)-R ａ or -SO ２ -R ｂ represents a group represented by R ａ and R ｂ are each independently Hydrogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, or It represents a monovalent heterocyclic group which may have a substituent. In formulas (Z-1) to (Z-4), the two R's may be the same or different.

4. preparing a support substrate having a first electrode provided thereon; A step of producing a film by the film producing method according to claim 3 to form an active layer; forming a second electrode; A method for producing an organic photoelectric conversion element, comprising the steps of:

5. A method of manufacturing a semiconductor device comprising the steps of: preparing a support substrate having a first electrode; A step of producing a film by the film producing method according to claim 3 to form an active layer; forming a second electrode; A method for manufacturing a light detecting element, comprising the steps of:

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