Photoelectric conversion element and optical sensor

Abstract

To provide a photoelectric conversion element and an optical sensor that can detect light with high sensitivity over a wide wavelength range in the long wavelength range.SOLUTION: A photoelectric conversion element includes an anode, a cathode, and an active layer located between the anode and the cathode, the active layer includes at least a first layer containing either a p-type semiconductor material or an n-type semiconductor material, and a second layer containing a semiconductor material of a type different from the semiconductor material contained in the first layer, and the maximum light absorption wavelength (λmax) of the active layer exceeds 1000 nm.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] A photoelectric conversion element is, for example, a device that is extremely useful from the viewpoints of energy saving and reduction of carbon dioxide emissions and has attracted attention.

[0003] A photoelectric conversion element is an element that includes at least a pair of electrodes including an anode and a cathode, and an active layer provided between the pair of electrodes. In the photoelectric conversion element, at least one of the pair of electrodes is made of a transparent or translucent material, and light is incident on the active layer from the transparent or translucent electrode side. Due to the energy (hν) of the light incident on the active layer, charges (holes and electrons) are generated in the active layer, and the generated holes move toward the anode, and the electrons move toward the cathode. Then, the charges that reach the anode and the cathode are taken out to the outside of the element.

[0004] For example, Non-Patent Document 1 and Non-Patent Document 2 disclose an organic photodetector (OPD) that photoelectrically converts light in the vicinity of the visible light region.

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the reports so far, the knowledge about photoelectric conversion elements for light in the long wavelength band has been limited. The present disclosure has been made in view of the above, and the present disclosure relates to providing a photoelectric conversion element and a photosensor having a wide wavelength band that can be detected with high sensitivity in the long wavelength band.

Means for Solving the Problems

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

[0008]

Chemical formula

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

[0010] [Chemical formula]

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

[0012]

Chemical formula

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

[0014]

Chemical formula

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

Advantages of the Invention

[0016] According to the present disclosure, there are provided a photoelectric conversion element and a photosensor that can detect with high sensitivity in a wide wavelength band in the long wavelength band.

Brief Description of the Drawings

[0017]

Figure 1

Embodiments for Carrying Out the Invention

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

[0019] Hereinafter, the photoelectric conversion element of the present disclosure will be described with reference to the drawings. Note that the drawings only schematically show the shapes, sizes, and arrangements of the constituent elements to the extent that the invention can be understood. The present disclosure is not limited by the following description, and each constituent element can be appropriately changed without departing from the gist of the present disclosure. Also, the configuration of the present disclosure is not necessarily manufactured or used in the arrangement shown in the drawings.

[0020] In the present disclosure, in the numerical range indicated by “~”, the numerical values described before and after “~” are included as the lower limit value and the upper limit value, respectively. In the numerical ranges described step by step in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. Also, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, the content rate of each component in the composition means the total content rate of the plurality of substances corresponding to each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In the present disclosure, when a plurality of elements are listed using “or” or “alternatively”, unless otherwise specified, the selection of combining a plurality of elements is not excluded as long as there is no technical contradiction. Even when an element is described in the singular in the present disclosure, unless otherwise specifically stated, a plurality of such elements are not excluded as long as there is no technical contradiction. In the present disclosure, a plurality of exemplary embodiments described separately may be combined with each other to form a new embodiment as long as they do not contradict each other.

[0021] In the present disclosure, commonly used terms are explained. In the description of the present disclosure, unless otherwise specifically stated, the following explanations apply.

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

[0023] The term "π-conjugated system" means a system in which π electrons are delocalized over multiple bonds.

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

[0025] The term "constituent unit" means a residue derived from a raw material compound (monomer) that is present in one or more in a compound and a polymer compound.

[0026] A "hydrogen atom" may be a light hydrogen atom or a deuterium atom.

[0027] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0028] The phrase "optionally having a substituent" includes both the case where all hydrogen atoms constituting a compound or a group are unsubstituted and the case where some or all of one or more hydrogen atoms are substituted by a substituent.

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

[0030] In the present specification, unless otherwise specified, the "alkyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkyl group, excluding the number of carbon atoms of the substituent, is usually preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. The number of carbon atoms of the branched or cyclic alkyl group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 50, more preferably 3 to 30, and even more preferably 4 to 20.

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

[0032] The alkyl group may have a substituent. The alkyl group having a substituent is, for example, a group in which a hydrogen atom in the above-exemplified alkyl group is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

[0033] Specific examples of the alkyl group having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3-(4-methylphenyl)propyl group, a 3-(3,5-dihexylphenyl)propyl group, and a 6-ethyloxyhexyl group.

[0034] The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group, excluding the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0035] Examples of the cycloalkyl group include an alkyl group having no substituent such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, and a fluorine atom.

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

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

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

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

[0040] The "alkyloxy group" (alkoxy group) may be linear, branched, or cyclic. The number of carbon atoms of the linear alkyloxy group, excluding the carbon atoms of the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms of the branched or cyclic alkyloxy group, excluding the carbon atoms of the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0041] The alkyloxy group may have a substituent. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group, an n-decyloxy group, a 3,7-dimethyloctyloxy group, a 3-heptyldodecyloxy group, a lauryloxy group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0042] The cycloalkyl group of the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms of the cycloalkyloxy group, excluding the carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

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

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

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

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

[0047] The alkylthio group may have a substituent. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

[0048] The cycloalkyl group 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, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0049] Examples of the cycloalkylthio group that may have a substituent include a cyclohexylthio group.

[0050] The number of carbon atoms of the "arylthio group", excluding the number of carbon atoms of the substituent, is usually preferably 6 to 60, more preferably 6 to 48.

[0051] The arylthio group may have a substituent. Examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group (C1-C12 indicates that the number of carbon atoms of the group described immediately after it is 1 to 12. The same applies hereinafter.), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

[0052] The "heterocyclic group" means a remaining atomic group obtained by removing any number of hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting a ring from a heterocyclic compound that may have a substituent.

[0053] The heterocyclic group may further have a substituent. The number of carbon atoms of the heterocyclic group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 30, more preferably 2 to 6.

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

[0055] The "aromatic heterocyclic group" means a remaining atomic group obtained by removing any number of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting the ring from an aromatic heterocyclic compound which may have a substituent. The aromatic heterocyclic group may further have a substituent.

[0056] The aromatic heterocyclic compounds include, in addition to compounds in which the heterocyclic ring itself exhibits aromaticity, compounds in which an aromatic ring is fused to the heterocyclic ring even if the heterocyclic ring itself does not exhibit aromaticity.

[0057] Specific examples of the compounds in which the heterocyclic ring itself exhibits aromaticity among the aromatic heterocyclic compounds include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

[0058] Specific examples of the compounds in which the aromatic heterocyclic ring itself does not exhibit aromaticity and an aromatic ring is fused to the heterocyclic ring among the aromatic heterocyclic compounds include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0059] The number of carbon atoms of the monovalent heterocyclic group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 60, more preferably 4 to 20.

[0060] The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, or the like.

[0061] The "substituted amino group" means an amino group having a substituent. Examples of the substituent that the amino group has include an alkyl group, an aryl group, and a monovalent heterocyclic group, and an alkyl group, an aryl group, or a monovalent heterocyclic group is preferable. The number of carbon atoms of the substituted amino group is usually preferably 2 to 30.

[0062] Examples of the substituted amino group include dialkylamino groups such as dimethylamino group and diethylamino group; diarylamino groups such as diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl)amino group, and bis(3,5-di-tert-butylphenyl)amino group.

[0063] The "acyl group" may have a substituent. The number of carbon atoms of the acyl group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 20, and more preferably 2 to 18. Specific examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group.

[0064] The "imine residue" means the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom or nitrogen atom constituting the carbon atom-nitrogen atom double bond from an imine compound. The "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of the imine compound include aldimine, ketimine, and a compound in which a hydrogen atom bonded to the nitrogen atom constituting the carbon atom-nitrogen atom double bond in the aldimine is substituted with an alkyl group or the like.

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

[0066]

Chemical formula

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

[0068] The "acid imide group" means the remaining atomic group after removing one hydrogen atom bonded to the nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is usually preferably 4 to 20. Specific examples of the acid imide group include groups represented by the following structural formulas. In the following structural formulas, Me represents a methyl group.

[0069]

Chemical formula

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

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

[0072] The "substituted sulfonyl group" means a group represented by -SO2-R X Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0073] The "substituted oxysulfonyl group" means a group represented by -(SO2)-O-R X or -O-(SO2)-R X Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0074] The number of carbon atoms of the substituted oxycarbonyl group, excluding the carbon atoms of the substituent, is usually preferably 2 to 60, more preferably 2 to 48.

[0075] Specific examples of the substituted oxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group.

[0076] The "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms in the linear alkenyl group, excluding the number of carbon atoms in the substituent, is usually preferably 2 to 30, more preferably 3 to 20. The number of carbon atoms in the branched or cyclic alkenyl group, excluding the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 4 to 20.

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

[0078] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group, excluding the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0079] Examples of the cycloalkenyl group include cycloalkenyl groups having no substituent such as cyclohexenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0080] Examples of the cycloalkenyl group having a substituent include methylcyclohexenyl group and ethylcyclohexenyl group.

[0081] The "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms in the linear alkynyl group, excluding the number of carbon atoms in the substituent, is usually preferably 2 to 20, more preferably 3 to 20. The number of carbon atoms in the branched or cyclic alkynyl group, excluding the number of carbon atoms in the substituent, is usually preferably 4 to 30, more preferably 4 to 20.

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

[0083] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group, excluding the number of carbon atoms in the substituent, is usually preferably 4 to 30, more preferably 12 to 19.

[0084] Examples of the cycloalkynyl group include cycloalkynyl groups having no substituent such as a cyclohexynyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, alkyloxy group, aryl group, or fluorine atom.

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

[0086] The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group, excluding the number of carbon atoms in the substituent, is usually preferably 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0087] The symbol "*" that can be attached to a chemical formula represents a bond. The dotted line in the chemical formula also indicates a bond. When two "*" and dotted lines are included in the chemical formula, there is no particular limitation on which of the two units to which the bond is attached.

[0088] "Ink" means a liquid substance used in a coating method and is not limited to a colored liquid. Further, the "coating method" includes a method of forming a film (layer) using a liquid substance, and examples thereof include a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a gravure printing method, a flexographic printing method, an offset printing method, an inkjet coating method, a dispenser printing method, a nozzle coating method, and a capillary coating method.

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

[0090] The "absorption peak wavelength" is a parameter specified based on the absorption peak of an absorption spectrum measured in a predetermined wavelength range, and refers to the wavelength of the absorption peak having the largest absorbance among the absorption peaks of the absorption spectrum.

[0091] The "external quantum efficiency" is also referred to as EQE (External Quantum Efficiency) and is a value indicating, as a ratio (%), the number of electrons that could be extracted outside the photoelectric conversion element out of the electrons generated with respect to the number of photons irradiated to the photoelectric conversion element.

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

[0093] The photoelectric conversion element of the present disclosure is a photoelectric conversion element having a wide wavelength band that can be detected with high sensitivity in the long wavelength band. Although the operation of the photoelectric conversion element of the present disclosure is not clear, it is presumed as follows. The active layer of the present disclosure has a Planar Hetero Junction structure (PHJ structure) having at least a first layer and a second layer. The first layer contains either a p-type semiconductor material or an n-type semiconductor material. That is, the first layer is a single film (also referred to as a single layer) containing only either a p-type semiconductor material or an n-type semiconductor material. On the other hand, the second layer contains a semiconductor material of a type different from the semiconductor material contained in the first layer. That is, the second layer is either a single film containing only either a p-type semiconductor material or an n-type semiconductor material, or a mixed film (also referred to as a mixed layer) containing both a p-type semiconductor material and an n-type semiconductor material. Here, when the overlap of the semiconductor material molecules in the active layer is regular, the semiconductor material can absorb light of a longer wavelength, and furthermore, the wavelength band that can be absorbed at a high absorbance becomes wider. Therefore, when the active layer of the photoelectric conversion element of the present disclosure has a single film in the active layer like the first layer, the semiconductor material can absorb light of a longer wavelength, and furthermore, the wavelength band that can be absorbed at a high absorbance becomes wider. On the other hand, in a mixed film containing both a p-type semiconductor material and an n-type semiconductor material, the p-type semiconductor material and the n-type semiconductor material are in a mixed state. That is, in the mixed film, the molecules of the p-type semiconductor material and the molecules of the n-type semiconductor material are irregularly intertwined with each other, and the regular overlap of the molecules is inhibited. Therefore, in the mixed film, the semiconductor material cannot absorb light of a longer wavelength, and the wavelength band that can be absorbed at a high absorbance becomes narrower.

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

[0095] In addition, the photoelectric conversion element of the present disclosure also includes a photoelectric conversion element having a wide wavelength band that can be detected with high sensitivity in the short wavelength band. In the short wavelength band, the active layer in the photoelectric conversion element having a wide wavelength band that can be detected with high sensitivity has a PHJ structure having at least the first layer and the second layer as described above. At the interface between the first layer and the second layer, the p-type semiconductor material and the n-type semiconductor material overlap, whereby the absorption wavelength band in the short wavelength band becomes wider.

[0096] For the above reasons, the photoelectric conversion element of the present disclosure becomes a photoelectric conversion element having a wide wavelength band that can be detected with high sensitivity in the long wavelength band. Note that the present disclosure is not limited to the above estimation mechanism at all.

[0097] Here, a configuration example that the photoelectric conversion element of the present disclosure can take will be described. FIG. 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure. Note that FIG. 1 is a diagram for illustrative purposes and does not limit the embodiments of the present disclosure.

[0098] As shown in FIG. 1, the photoelectric conversion element 10 is preferably provided on the support substrate 11. The photoelectric conversion element 10 includes an anode 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 anode 12, an active layer 19 provided so as to be in contact with the hole transport layer 13, an electron transport layer 16 provided so as to be in contact with the active layer 19, and a cathode 17 provided so as to be in contact with the electron transport layer 16. Preferably, a sealing member 18 is further provided so as to be in contact with the cathode 17. The active layer 19 preferably consists of a first layer 14 and a second layer 15. The first layer 14 is preferably provided so as to be in contact with the hole transport layer 13, and the second layer 15 is preferably provided so as to be in contact with the electron transport layer 16.

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

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

[0101] As a photoelectric conversion element of still another configuration example, it includes an anode provided so as to be in contact with a support substrate, an active layer provided so as to be in contact with the anode, an electron transport layer provided so as to be in contact with the active layer, and a cathode provided so as to be in contact with the electron transport layer. The active layer has at least a first layer and a second layer. The first layer may be provided so as to be in contact with either the anode or the electron transport layer, and the second layer may also be provided so as to be in contact with either the anode or the electron transport layer.

[0102] Hereinafter, the components that can be included in the photoelectric conversion element of the present disclosure will be specifically described.

[0103] <Active layer> The active layer of the present disclosure exists between the anode and the cathode described later. The active layer of the present disclosure may exist in contact in the order of the anode, the active layer, and the cathode in the vertical direction, or may exist in contact in the order of the anode, the hole transport layer, the active layer, the electron transport layer, and the cathode in the vertical direction as shown in FIG. 1 or FIG. 2.

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

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

[0106] The method for preparing the measurement sample is as follows.

[0107] - Preparation of Ink - With respect to 1,2-dimethylbenzene as a solvent, a p-type semiconductor material (polymer compound) is stirred at 60°C for 8 hours so as to have a concentration of 1% by mass with respect to the total mass of the ink, and the obtained mixture is filtered using a filter to obtain an ink containing the p-type semiconductor material. With respect to toluene as a solvent, an n-type semiconductor material (polymer compound) is stirred at 60°C for 8 hours so as to have a concentration of 1% by mass with respect to the total mass of the ink, and the obtained mixture is filtered using a filter to obtain an ink containing the n-type semiconductor material. For a solvent (chloroform and chloronaphthalene mixed at a volume ratio of 98:2), the n-type semiconductor material was stirred at room temperature for 8 hours so that its concentration was 1% by mass based on the total mass of the ink, and the p-type semiconductor material was also stirred at room temperature for 8 hours so that its concentration was 1% by mass based on the total mass of the ink. The resulting mixture was filtered using a filter to obtain an ink containing the n-type semiconductor material and the p-type semiconductor material.

[0108] -Fabrication of the active layer- An ink containing the n-type semiconductor material and / or the p-type semiconductor material was applied onto a cleaned glass substrate by spin coating to form a coating film. After that, it was heat-treated for 5 minutes using a hot plate heated to 70 °C under the atmosphere to dry it (pre-baking process). Then, it was heat-treated at 100 °C for 10 minutes on the hot plate in the atmosphere (post-baking process) to form the first layer. Next, an ink containing the n-type semiconductor material and / or the p-type semiconductor material was applied onto the fabricated first layer by spin coating to form a coating film. After that, it was heat-treated for 5 minutes using a hot plate heated to 70 °C under the atmosphere to dry it (pre-baking process). Then, it was heat-treated at 100 °C for 10 minutes on the hot plate in the atmosphere (post-baking process) to form the second layer and fabricate the PHJ film (active layer).

[0109] -Measurement- For the measurement of the optical absorption wavelength, a spectrophotometer operating in the wavelength regions of ultraviolet light, visible light, and near-infrared light (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian) was used.

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

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

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

[0113] The light absorption end wavelength of the active layer is represented as the wavelength value at the long wavelength side end of the light absorption wavelength. In the present disclosure, the numerical value of the light absorption end wavelength is specifically represented by the value obtained by the following method.

[0114] The method for preparing the measurement sample can be carried out in the same manner as the method for preparing the ink and the method for forming the active layer in the measurement of the light absorption maximum wavelength of the active layer.

[0115] -Measurement- For the measurement of the light absorption wavelength, a spectrophotometer that operates in the wavelength region of ultraviolet light, visible light, and near-infrared light (for example, the ultraviolet-visible-near-infrared spectrophotometer "Cary5E" manufactured by Varian) is used.

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

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

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

[0119] -First reference line- In the entire absorption waveform (absorption spectrum), the absorbance of the absorption peak point (maximum value) closest to the long wavelength is set to 100%.

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

[0121] Of the two intersections where a straight line parallel to the wavelength axis showing 44% of the absorbance of the absorption peak point intersects the absorption waveform, the intersection closer to the long wavelength than the absorption peak point is taken as the second point. The straight line connecting the first point and the second point is taken as the first reference line.

[0122] -Second reference line- In the entire absorption waveform, the absorbance of the absorption peak point (maximum value) closest to the long wavelength is set to 100%.

[0123] Of the two intersections where a straight line parallel to the wavelength axis showing an absorbance of 20% of the absorption peak point intersects the absorption waveform, a point on the absorption waveform that is 200 nm longer in wavelength than the wavelength of the intersection closer to the longer wavelength side than the absorption peak point is defined as the third point, with the wavelength of the intersection as the reference point. Also, a point on the absorption waveform that is 250 nm longer in wavelength than the wavelength of the reference point is defined as the fourth point. A straight line connecting the third point and the fourth point is defined as the second reference line.

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

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

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

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

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

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

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

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

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

[0133] In the present disclosure, the HOMO energy and the LUMO energy can be calculated by any conventionally known and suitable computational scientific method. Specifically, they are obtained from the following equations. LUMO energy = energy band gap (Eg) - HOMO energy Band gap (Eg) = hc / optical absorption edge wavelength

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

[0135]

Chemical formula

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

[0137]

Chemical formula

[0138] In formula (A-1), Ar represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring, and the carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a condensed ring. When the carbocyclic ring or the heterocyclic ring has a plurality of substituents, the plurality of substituents may be the same or different.

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

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

[0141] D preferably has at least one monovalent side chain R D1 bonded to the sp3 carbon or the sp3 silicon. D preferably has 1 to 4 monovalent side chains R D1 bonded to the sp3 carbon or the sp3 silicon, more preferably 1 or 2, and even more preferably 2. As described above, the main skeleton of the monocyclic ring or the condensed ring constituting the aromatic group in D preferably has at least one of sp3 carbon and sp3 silicon, and D has a monovalent side chain R D1Preferably having at least one. Thereby, the molecules of the compound which is an n-type semiconductor material, the side chain R with respect to the main skeleton of D (i.e., the π plane) D1 has a structure in which it protrudes in the vertical direction, and the compound represented by the formula (1) of the present disclosure is less likely to form H aggregates and more likely to form J aggregates in the formed thin film.

[0142] - Side chain R D1 -[[]]END]] The side chain R in D D1 are each independently a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substitutedoxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, A cycloalkynyl group which may have a substituent, a cyano group, or a nitro group.

[0143] The side chain R in D D1 is not particularly limited in its specific structure. The side chain R in D D1 is each independently preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent, more preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and even more preferably an alkyl group.

[0144] -Chemical Structure of -D From the viewpoint that the compound easily absorbs light of a long wavelength, in the formula (1), D is preferably a group represented by the following formula (D-1) or the following formula (D-2). In the following formula (D-1) and formula (D-2), the symbol "*" represents a bond with (L1) m in the formula (1) or a bond with (L2) n in the formula (1).

[0145]

Chemical formula

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

[0147]

Chemical formula

[0148] In the formula (X-1) to formula (X-6), the definition of R D2 is each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, A cycloalkyl group which may have a substituent, An aryl group which may have a substituent, An alkyloxy group which may have a substituent, A cycloalkyloxy group which may have a substituent, An aryloxy group which may have a substituent, An alkylthio group which may have a substituent, A cycloalkylthio group which may have a substituent, An arylthio group which may have a substituent, A monovalent heterocyclic group which may have a substituent, A substituted amino group which may have a substituent, An acyl group which may have a substituent, An imine residue which may have a substituent, An amide group which may have a substituent, An acid imide group which may have a substituent, A substituted carbonyl group which may have a substituent, A substituted oxycarbonyl group which may have a substituent, A substituted sulfonyl group which may have a substituent, A substitutedoxysulfonyl group which may have a substituent, An alkenyl group which may have a substituent, A cycloalkenyl group which may have a substituent, An alkynyl group which may have a substituent, A cycloalkynyl group which may have a substituent, A cyano group, or A nitro group.

[0149] In each of Formula (X-1) to Formula (X-6), when there are two Rs D2 the two Rs D2 may be the same as or different from each other. From the perspective that the compound is likely to absorb light of a long wavelength, X is preferably any group represented by Formula (X-1) to Formula (X-4), and more preferably any group represented by Formula (X-1), Formula (X-3), or Formula (X-4). In Formulas (X-1) to (X-6), R D2 preferred embodiment is a hydrogen atom or the aforementioned R D1 preferred embodiment is the same as that of.

[0150] In Formula (D-2), Ar 1 and Ar 2 each independently represents an aromatic carbon ring which may have a substituent and in which a plurality of ring structures may be further condensed, or an aromatic heterocyclic ring which may have a substituent and in which a plurality of ring structures may be further condensed. Either Ar 1 or Ar 2 may not be present.

[0151] Ar 1 and Ar 2 The aromatic heterocyclic rings that can constitute include, in addition to monocyclic and condensed rings in which the heterocyclic ring itself exhibits aromaticity, rings in which an aromatic ring is condensed to the heterocyclic ring even if the heterocyclic ring itself that constitutes the ring does not exhibit aromaticity.

[0152] Ar 1 and Ar 2 The aromatic heterocyclic rings that can constitute may each be a monocyclic ring or a condensed ring. When the aromatic heterocyclic ring is a condensed ring, the condensed ring may be a condensed ring in which all of the rings constituting the condensed ring have aromaticity, or a condensed ring in which only a part has aromaticity. When these rings have a plurality of substituents, these substituents may be the same or different.

[0153] Ar 1 and Ar 2Specific examples of the aromatic carbon ring that can constitute include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, and phenanthrene ring. Preferably, they are benzene ring and naphthalene ring, more preferably benzene ring and naphthalene ring, and even more preferably benzene ring. These rings may have substituents.

[0154] Ar 1 and Ar 2 Specific examples of the aromatic heterocyclic ring that can constitute 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, and also phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring. These rings may have substituents.

[0155] -Examples of -D- Examples of formula (D-1) include groups represented by the following formula (d-1-1) to formula (d-1-7). Examples of formula (D-2) include groups represented by the following formula (d-2-1) to formula (d-2-10). In formula (d-1-1) to formula (d-1-7) and formula (d-2-1) to formula (d-2-10), the definition of R D2 is, independently of each other, the same as the definition of R D2 described above. In the following formula (d-2-1) to formula (d-2-10), U is, independently of each other, S, SiR D2 2, Se, NR D2 , or O. U is preferably S. In the following formula (d-1-1) to formula (d-1-7) and formula (d-2-1) to formula (d-2-10), the symbol "*" indicates a bond with (L1) in formula (1) m or a bond with (L2) n .

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

[0157]

Chem.

[0158]

Chem.

[0159] -Specific Examples of -D Specific examples of D include groups represented by the following formulas. In each formula, the symbol "*" represents the bond with (L1) in formula (1) m or the bond with (L2) n .

[0160]

Chem.

[0161] 〔(L1) m ; linker connecting A1 and D〕 (L1) in formula (1) m When m is 2 or more in formula (1), multiple L1s present in formula (1) are each independently defined in terms of their chemical structure. That is, the descriptions of L1 given below are for each independent L1.

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

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

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

[0165] The element capable of non-covalent interaction with an element in an adjacent unit that the aromatic group in L1 has is preferably at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, more preferably at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, and a nitrogen atom, and still more preferably at least one of a sulfur atom and an oxygen atom.

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

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

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

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

[0170] As described above, when the aromatic group in L1 has an element capable of non-covalent interaction with an element in an adjacent unit, a non-covalent crosslink is formed between the element in L1 and the unit (A1, L1, or D) present adjacent to L1. That is, in the formed thin film, the planarity of the main skeleton (i.e., the π plane) of the monocyclic or condensed ring constituting the aromatic group in L1 is likely to be maintained.

[0171] - Side chain R L1 - The side chain R in L1 L1 is each independently a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, A monocyclic heterocyclic group which may have a substituent, A substituted amino group which may have a substituent, An acyl group which may have a substituent, An imine residue which may have a substituent, An amide group which may have a substituent, An acid imide group which may have a substituent, A substituted carbonyl group which may have a substituent, A substituted oxycarbonyl group which may have a substituent, A substituted sulfonyl group which may have a substituent, A substituted oxysulfonyl group which may have a substituent, An alkenyl group which may have a substituent, A cycloalkenyl group which may have a substituent, An alkynyl group which may have a substituent, A cycloalkynyl group which may have a substituent, A cyano group, or A nitro group.

[0172] From the viewpoint that the compound easily absorbs light of a long wavelength, the side chain R in L1 L1 is each independently preferably an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, a substituted amino group which may have a substituent, an alkyl group which may have a substituent, or a halogen atom, more preferably an alkyloxy group which may have a substituent or a halogen atom, and even more preferably an alkyloxy group which may have a substituent.

[0173] -Chemical Structure of -L1- From the viewpoint that the compound easily absorbs light of a long wavelength, in the formula (1), L1 is preferably any group represented by the following formula (L1-1) to formula (L1-7), more preferably any group represented by the following formula (L1-1) to formula (L1-4), and even more preferably the group represented by the following formula (L1-1). That is, from the viewpoint that the compound is likely to absorb light of a long wavelength, L1 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0174]

Chemical formula

[0175] In formulas (L1-1) to (L1-7), R L11 is, independently of each other, preferably further has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom in addition to the definition of the above R D2 . As described above, when R L11 has at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, and the unit adjacent to L1 having R L11 has an element capable of having a non-covalent interaction with at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, a fluorine atom, a nitrogen atom, a selenium atom, and a phosphorus atom, a non-covalent crosslink is formed between R L11 and the unit adjacent to L1 having R L11 . That is, in the formed thin film, the planarity of the main skeleton (i.e., the π plane) of the monocyclic or condensed ring constituting the aromatic group in L1 is easily maintained.

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

[0177]

Chemical formula

[0178] -m- In formula (1), m is an integer of any one of 1 to 4. From the viewpoints of the compound being likely to absorb light of a long wavelength and ease of synthesis, m is preferably an integer of any one of 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0179] -(L1) m Specific examples of - (L1) m Specific examples of (L1) include, in addition to the specific examples of L1 described above (that is, the specific examples when m is 1 in (L1) m ), groups represented by the following formulas.

[0180]

Chemical formula

[0181]

Chemical formula

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

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

[0184] [(L2) n ; a linker connecting A2 and D (L2) in formula (1) n In the case where n is an integer of 2 or more in formula (1), when there are a plurality of L2s in formula (1), the chemical structure of each L2 is independently defined. That is, the following description of L2 is for each independent L2.

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

[0186] - Chemical structure of L2 - From the viewpoint that the compound easily absorbs light with a long wavelength, in the above formula (1), each L2 is preferably any group represented by the following formula (L2-1) to formula (L2-12), more preferably any group represented by the following formula (L2-1) to formula (L2-9), and even more preferably any group represented by the following formula (L2-1) to formula (L2-7). That is, from the viewpoint that the compound easily absorbs light with a long wavelength, L2 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure. From the viewpoint of the ease of J-aggregation of the compounds of the present disclosure, the chemical structure of L2 is not more restricted than the chemical structure of L1.

[0187] [Chemical formula]

[0188] In formulas (L2-1) to (L2-12), the plurality of Rs L2 are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group.

[0189] -Specific examples of -L2- As a specific example of L2, in addition to the specific examples of L1 described above, a group represented by the following formula can be further mentioned.

[0190]

Chemical formula

[0191] -n- In formula (1), n is an integer of any one of 0 to 4. That n is 0 means that (L2) n does not exist, and it means that D and A2 in formula (1) are directly bonded. From the viewpoints of the compound being likely to absorb light of a long wavelength and ease of synthesis, n is preferably an integer of 1 or more, may be an integer of 2 or more, more preferably an integer of any one of 1 to 4, still more preferably an integer of any one of 1 to 3, even more preferably 1 or 2, and most preferably 1.

[0192] -(L2) n Specific examples of (L2) n As specific examples of (L2), in addition to the specific examples of L2 described above (that is, the specific examples when n is 1 in (L2) n ) and the specific examples of (L1) m described above, a group represented by the following formula can be further mentioned.

[0193]

Chemical formula

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

[0195] In formula (1), when taking D in formula (1) as the center point, the chemical structure of (L1) m and (L2) nThe chemical structure may be point-symmetric or asymmetric. From the viewpoint that the compound is likely to absorb light with a long wavelength, in formula (1), it is preferable that m is 2 and n is 1 or 2.

[0196] 〔A1 and A2; acceptor〕 In formula (1), A1 and A2 are each independently a group represented by the following formula (A-1). In each formula, the dotted line represents the bond with (L1) in formula (1) m or the bond with (L2) n shown.

[0197]

Chemical formula

[0198] In formula (A-1), Ar represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. The carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a condensed ring. When the carbocyclic ring or the heterocyclic ring has a plurality of substituents, the plurality of substituents may be the same or different.

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

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

[0201] -Chemical structures of A1 and A2 In formula (1), A1 and A2 are each independently preferably any group represented by the following formula (a-1) to formula (a-8). In each formula, the symbol "*" is (L1) in formula (1). m the bond with or (L2) n the bond with indicates. The chemical structures of A1 and A2 may be the same as or different from each other. From the viewpoint of ease of compound synthesis, the chemical structures of A1 and A2 are preferably the same.

[0202]

Chemical formula

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

[0204] -Specific examples of A1 and A2 Specific examples of A1 and A2 include groups represented by the following formulas. In each formula, the symbol "*" represents a bond with (L1) in formula (1) m or a bond with (L2) n .

[0205] [Chemical formula]

[0206] [Specific examples of the compound represented by formula (1) of the present disclosure] Preferable specific examples of the compound represented by formula (1) of the present disclosure include compounds represented by the following formulas.

[0207] [Chemical formula]

[0208] [Chemical formula]

[0209] [Chemical formula]

[0210] [Chemical formula]

[0211] [Chemical formula]

[0212] [Chemical formula]

[0213] [Chemical formula]

[0214] -Other n-type semiconductor materials- As the n-type semiconductor material, the compound represented by the above formula (1) may be used alone, or may be two or more n-type semiconductor materials represented by the above formula (1), or may include an n-type semiconductor material other than the compound represented by the above formula (1).

[0215] Examples of the low molecular weight compound that can be included as an n-type semiconductor material other than the compound represented by the above formula (1) include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and phenanthrene derivatives such as bathocuproine.

[0216] Examples of the high molecular weight compound that can be included as an n-type semiconductor material include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

[0217] Also, the other compound may be a fullerene derivative.

[0218] Here, the fullerene derivative refers to a compound in which at least a part of fullerene (C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene, and C 84 Fullerene) is modified. In other words, it refers to a compound having one or more groups added to the fullerene skeleton. Hereinafter, particularly C 60Fullerene and fullerene derivatives are referred to as "C" 60 fullerene derivatives, and C 70 Fullerene and fullerene derivatives are sometimes referred to as "C" 70 fullerene derivatives.

[0219] Fullerene derivatives that can be included as n-type semiconductor materials are not particularly limited as long as they do not impair the object of the present disclosure.

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

[0221]

Chemical formula

[0222] In the formula of the above C 60 fullerene derivative, R is a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, a cycloalkyloxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, a cycloalkylthio group that may have a substituent, an arylthio group that may have a substituent, a monovalent heterocyclic group that may have a substituent, a substituted amino group that may have a substituent, an acyl group that may have a substituent, an imine residue that may have a substituent, an amide group that may have a substituent, an acid imide group that may have a substituent, An optionally substituted carbonyl group, An optionally substituted oxycarbonyl group, An optionally substituted sulfonyl group, An optionally substitutedoxysulfonyl group, An optionally substituted alkenyl group, An optionally substituted cycloalkenyl group, An optionally substituted alkynyl group, An optionally substituted cycloalkynyl group, A cyano group, or A nitro group. When there are a plurality of Rs, the plurality of Rs may be the same as or different from each other.

[0223] C 70 Examples of the fullerene derivative include the following compounds.

[0224]

Chemical formula

[0225] (p-type semiconductor material) Regarding the preferred p-type semiconductor material when the semiconductor material contained in the first layer is a p-type semiconductor material, the definition, examples, preferred embodiments, etc. are the same as those of the p-type semiconductor material in the [second layer] described later, including definitions, examples, and preferred embodiments.

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

[0227] (n-type semiconductor material) Regarding the preferred n-type semiconductor materials when the second layer contains an n-type semiconductor material, including definitions, examples, and preferred embodiments, etc., they are the same as those of the n-type semiconductor materials in [the first layer].

[0228] (p-type semiconductor material) The second layer preferably contains a p-type semiconductor material, and from the viewpoint of improving the high photoelectric conversion efficiency, it is preferable that the p-type semiconductor material is a hole transport material.

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

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

[0231] From the viewpoint of particularly improving the solubility in a solvent, the weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3000 or more and 500000 or less.

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

[0233] Here, the donor structural unit is a structural unit with excessive π electrons, and the acceptor structural unit is a structural unit lacking π electrons.

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

[0235] Examples of the p-type semiconductor material that is a high molecular compound 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, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and polyfluorene and its derivatives.

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

[0237]

Chemical formula

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

[0239]

Chemical formula

[0240] In formula (Z-1) to formula (Z-7), the definition of R is the same as the definition of R in the formula of the fullerene derivative. 60 In each of formula (Z-1) to formula (Z-7), when there are two Rs, the two Rs may be the same or different from each other.​

[0241] Ar 3 and Ar 4 Examples of the aromatic heterocyclic ring that can form Ar and Ar include, in addition to monocyclic and condensed rings in which the heterocyclic ring itself exhibits aromaticity, rings in which an aromatic ring is condensed to the heterocyclic ring even if the heterocyclic ring itself that forms the ring does not exhibit aromaticity.

[0242] Ar 3 and Ar 4 The aromatic heterocyclic rings that can form Ar and Ar may each be a monocyclic ring or a condensed ring. When the aromatic heterocyclic ring is a condensed ring, the condensed ring may be a condensed ring in which all of the rings that form the condensed ring have aromaticity, or a condensed ring in which only some of them have aromaticity. When these rings have a plurality of substituents, these substituents may be the same or different.

[0243] Ar 3 and Ar 4 Specific examples of the aromatic carbon ring that can form Ar and Ar include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, and phenanthrene ring, preferably benzene ring and naphthalene ring, more preferably benzene ring and naphthalene ring, and even more preferably benzene ring. These rings may have substituents.

[0244] Specific examples of the aromatic heterocyclic ring include ring structures possessed by the compounds already described as aromatic heterocyclic compounds, such as 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, and phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring. These rings may have substituents.

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

[0246]

Chemical formula

[0247] In formula (3-1), (3-2) and (3-3), the definitions of Ar 3 , Ar 4 and R are the same as the definitions of Ar 3 , Ar 4 in formula (3) and the definition of R in the formula of the C 60 fullerene derivative.

[0248] Specific examples of the preferred structural unit represented by formula (3) include structural units represented by the following formulas.

[0249]

Chemical formula

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

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

[0252]

Chemical formula

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

[0254] Ar 5The number of carbon atoms in the divalent aromatic heterocyclic group represented by is preferably from 2 to 60, more preferably from 4 to 60, still more preferably from 4 to 20.

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

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

[0257]

Chemical formula

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

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

[0260] Note that the structural units represented by Formulas (4-1) to (4-10) can usually function as acceptor structural units as described above. However, it is not limited thereto, and in particular, the structural units represented by Formulas (4-4), (4-5) and (4-7) can also function as donor structural units.

[0261] The p-type semiconductor material preferably contains a structural unit containing a thiophene skeleton and is a π-conjugated polymer compound containing a π-conjugated system.

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

[0263]

Chemical formula

[0264]

Chemical formula

[0265]

Chemical formula

[0266]

Chemical formula

[0267] The polymer compound which is a p-type semiconductor material preferably contains a structural unit represented by Formula (3) as a donor structural unit and a structural unit represented by Formula (4) as an acceptor structural unit, and is a π-conjugated polymer compound.

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

[0269] The polymer compound which is a p-type semiconductor material may contain two or more structural units represented by the formula (3), and may contain two or more structural units represented by the formula (4).

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

[0271]

Chemical formula

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

[0273] Ar 6 The arylene group represented by means the remaining atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon includes a compound having a condensed ring, two or more selected from the group consisting of an independent benzene ring and a condensed ring, and a compound in which they are directly bonded or bonded via a divalent group such as a vinylene group.

[0274] Examples of the substituent which the aromatic hydrocarbon may have include the same substituents as the substituents exemplified as the substituents which the heterocyclic compound may have.

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

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

[0277]

Chem.

[0278]

Chem.

[0279]

Chem.

[0280]

Chem.

[0281]

Chem.

[0282]

Chem.

[0283]

Chem.

[0284]

Chem.

[0285] In the formula, the definition of R is C 60 It is the same as the definition of R in the formula of the fullerene derivative. A plurality of Rs may be the same or different.

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

[0287]

Chemical formula

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

[0289] The structural unit constituting the polymer compound which is a p-type semiconductor material may be a structural unit in which two or more structural units selected from the above structural units are combined and linked.

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

[0291] Specific examples of the polymer compound which is a p-type semiconductor material include polymer compounds represented by the following formulas (P-1) to (P-19).

[0292]

Chemical formula

[0293]

Chem.

[0294]

Chem.

[0295]

Chem.

[0296]

Chem.

[0297]

Chem.

[0298]

Chem.

[0299]

Chem.

[0300] In the above formula, the definition of R is the same as that of R in the formula of the fullerene derivative. A plurality of Rs may be the same as or different from each other. 60 When the above-exemplified polymer compound is used as the p-type semiconductor material, it is possible to suppress a decrease in EQE with respect to heat treatment in the manufacturing process of the photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, or to further improve the EQE, and it is possible to improve the heat resistance of the photoelectric conversion element.

[0301]

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

[0303] [Substrate] The photoelectric conversion element is preferably usually formed on a substrate (support substrate). Further, it may be sealed with a substrate (sealing substrate). Usually, one of a pair of electrodes including an anode and a cathode is formed on the substrate. The material of the substrate is not particularly limited as long as it does not chemically change when forming a layer containing an organic compound.

[0304] Examples of the material of the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, the electrode on the side opposite to the electrode provided on the opaque substrate side (in other words, the electrode far from the opaque substrate) is preferably a transparent or translucent electrode.

[0305] [Electrode] The photoelectric conversion element preferably includes an anode and a cathode which are a pair of electrodes. At least one of the anode and the cathode is preferably a transparent or translucent electrode for allowing light to enter.

[0306] Examples of materials for transparent or translucent electrodes include conductive metal oxide films and translucent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and composites thereof such as indium tin oxide (ITO), indium zinc oxide (IZO), and conductive materials such as NESA, gold, platinum, silver, and copper can be mentioned. As materials for electrodes that are transparent or translucent, ITO, IZO, and tin oxide are preferred. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives, etc. as the material may be used. The transparent or translucent electrode may be an anode or a cathode.

[0307] If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode with low light transmittance. Examples of materials for electrodes with low light transmittance include metals and conductive polymers. Specific examples of materials for electrodes 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, ytterbium, etc., and alloys of two or more of these, or alloys of one or more of these metals and 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. Examples of alloys include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

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

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

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

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

[0312] The hole transport layer contains a hole transporting material. Examples of the hole transporting material include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO3), and molybdenum oxide (MoO3). Examples of hole transporting material products include P-10 and P-21 from Avantama.

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

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

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

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

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

[0318] Examples of polyalkyleneimine and its derivatives include alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly polymers obtained by polymerizing one or more alkyleneimines having 2 to 4 carbon atoms by a conventional method, and polymers chemically modified by reacting them with various compounds. As polyalkyleneimine and its derivatives, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferable.

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

[0320] Examples of the metal oxide 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 zinc oxide is particularly preferable. Examples of the metal oxide products include Avantama's N-10, N-11, N-12, N-13, N-20X, N-21X, Infinity PV's ZnO, ZnO(2.8%), ZnO(5.6%), and Doped ZnO.

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

[0322] <Sealing member> The photoelectric conversion element of the present disclosure further includes a sealing member, and it is preferable to form a sealed body sealed by such a sealing member. As the sealing member, any suitable conventionally known member can be used. Examples of the sealing member include a combination of a glass substrate (sealing substrate) as a substrate and a sealing material (adhesive) such as a UV curable resin.

[0323] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of the layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

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

[0325] The sealing member is usually composed of a material that can withstand the heat treatment performed when the photoelectric conversion element is incorporated into a device such as the following application examples to which the photoelectric conversion element is applied.

[0326] <Applications of the photoelectric conversion element> Examples of the applications of the photoelectric conversion element of the present disclosure include a photodetector and a solar cell. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from the transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes, and can operate as a photodetector (photosensor). Also, by integrating a plurality of photodetectors, it can be used as an image sensor. Thus, the photoelectric conversion element of the present disclosure can be preferably used particularly as a photodetector.

[0327] In addition, the photoelectric conversion element of the present disclosure can generate a photoelectromotive force between the electrodes when irradiated with light, and can operate as a solar cell. By integrating a plurality of photoelectric conversion elements, a solar cell module can also be formed.

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

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

[0330] Since the compound of the present disclosure is included in the photoelectric conversion element of the present disclosure, it is driven at a longer wavelength than before.

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

[0332] The manufacturing method of the photoelectric conversion element of the present disclosure may include a step including a process of heating at a heating temperature of 100°C or higher. More specifically, the active layer may be formed by a step including a process of heating at a heating temperature of 100°C or higher, and / or a step including a process of heating at a heating temperature of 200°C or higher may be included after the step of forming the active layer.

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

[0334] (Step of preparing a substrate) In this step, for example, a support substrate provided with an anode is prepared. Also, a substrate provided with a conductive thin film formed of the electrode material described above is obtained from the market, and if necessary, the conductive thin film is patterned to form an anode, whereby a support substrate provided with an anode can be prepared.

[0335] In the manufacturing method of the photoelectric conversion element of the present disclosure, the method of forming the anode when forming the anode on the support substrate is not particularly limited. The anode can be formed on a configuration (e.g., support substrate, active layer, hole transport layer) on which the anode is to be formed by any suitable method known in the art, such as vacuum evaporation, sputtering, ion plating, plating, or coating, using the materials described above.

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

[0337] The method for forming the hole transport layer is not particularly limited. From the viewpoint of making the formation process of the hole transport layer simpler, it is preferable to form the hole transport layer by any conventionally known suitable coating method. The hole transport layer can be formed, for example, by a coating method using a coating solution containing the material and solvent of the hole transport layer already described, or by a vacuum evaporation method.

[0338] (Process for forming the active layer) In the method for manufacturing the photoelectric conversion element of the present disclosure, an active layer is formed on the hole transport layer. The active layer, which is a main component, can be formed by any conventionally known suitable formation process. It is preferable to manufacture the active layer by a coating method using an ink (coating solution) containing a semiconductor material. The preferred embodiments of the ink containing the semiconductor material are as described above.

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

[0340] Step (i) As a method for applying the ink to the object to be coated, any suitable coating method can be used. Preferred coating methods include a slit coating method, a knife coating method, a spin coating method, a microgravure coating method, a gravure coating method, a bar coating method, an inkjet printing method, a nozzle coating method, or a capillary coating method. More preferred are the slit coating method, the spin coating method, the capillary coating method, or the bar coating method. Even more preferred are the slit coating method or the spin coating method.

[0341] The ink for forming the active layer is applied to an application target selected according to the photoelectric conversion element and its manufacturing method. The ink for forming the active layer can be applied to a functional layer of the photoelectric conversion element in the manufacturing process of the photoelectric conversion element, which is a functional layer where the active layer can exist. Therefore, the application target of the ink for forming the active layer varies depending on the layer structure of the photoelectric conversion element to be manufactured and the order of layer formation. For example, when the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are laminated, and the layers described more to the left are formed first, the application target of the ink for forming the active layer is the hole transport layer. Also, for example, when the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are laminated, and the layers described more to the left are formed first, the application target of the ink for forming the active layer is the electron transport layer.

[0342] Step (ii) As a method for removing the solvent from the coating film of the ink, that is, a method for removing the solvent from the coating film and solidifying it, any suitable method can be used. Examples of the method for removing the solvent include drying methods such as directly heating using a hot plate in an inert gas atmosphere such as nitrogen gas, hot air drying method, infrared heating drying method, flash lamp annealing drying method, and vacuum drying method.

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

[0344] Regarding the implementation conditions of the pre-bake step and the post-bake step, that is, conditions such as the heating temperature and the heat treatment time, any suitable conditions can be set in consideration of the composition of the ink used, the boiling point of the solvent, etc.

[0345] Specifically, in the manufacturing method of the photoelectric conversion element of the present disclosure, for example, the pre-bake step and the post-bake step can be implemented using a hot plate in an air atmosphere or a nitrogen gas atmosphere.

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

[0347] The total heat treatment time in the pre-baking process and the post-baking process can be, for example, 1 hour.

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

[0349] The heat treatment time can be, for example, 10 minutes or more. The upper limit value of the heat treatment time is not particularly limited, but considering the tact time etc., it can be, for example, 4 hours.

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

[0351] The thickness of the active layer is not particularly limited. The thickness of the active layer can be made any suitable thickness in consideration of the balance between the suppression of the dark current and the extraction of the generated photocurrent. From the viewpoint of further reducing the dark current in particular, 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. Also, 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. Note that the above-preferred thickness of the active layer may be the thickness of one active layer or the total thickness of a plurality of active layers.

[0352] The step of forming the active layer may include other steps in addition to step (i) and step (ii) on the condition that the object and effect of the present disclosure are not impaired.

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

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

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

[0356] The method for forming the electron transport layer is not particularly limited. From the viewpoint of making the formation process of the electron transport layer simpler, it is preferable to form the electron transport layer by any conventionally known suitable coating method or vacuum evaporation method.

[0357] (Step of forming the cathode) The method for forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by any conventionally known suitable method such as a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, or a plating method using, for example, the materials of the electrodes exemplified above. It is preferable that the photoelectric conversion element of the present disclosure is manufactured by the above steps.

[0358] (Step of forming the sealing body) In forming the encapsulant, any conventionally known suitable encapsulant (adhesive) and substrate (encapsulation substrate) are used. Specifically, after applying an encapsulant such as a UV curable resin on a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then bonding them together without any gaps with the encapsulant, a photoelectric conversion element is encapsulated in the gap between the support substrate and the encapsulation substrate by using a method suitable for the selected encapsulant such as irradiation with UV light, whereby an encapsulant of the photoelectric conversion element can be obtained.

[0359] <Photo-detection element> The photoelectric conversion element of the present disclosure, particularly a photo-detection element (photo-sensor), can function when incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device) as described above.

[0360] Such an image sensor or biometric authentication device can be manufactured by a manufacturing method including a process including a treatment in which the photoelectric conversion element (encapsulant of the photoelectric conversion element) is heated at a heating temperature of 100°C or higher.

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

Example

[0362] Hereinafter, examples are shown to explain the present disclosure in more detail. The present disclosure is not limited to the examples described below.

[0363] <Fabrication of active layer> An active layer was fabricated using a p-type semiconductor material and an n-type semiconductor material.

[0364] [p-type semiconductor material] The polymer compound shown in Table 1 below was used as the p-type semiconductor material (electron-donating compound).

[0365]

Table 1

[0366] The polymer compound P-1, which is a p-type semiconductor material, was obtained from the market and used as PCE10 / PTB7-Th (trade name, manufactured by 1-material). The polymer compound P-2, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2013 / 051676. The polymer compound P-3, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2011 / 052709. The polymer compound P-4, which is a p-type semiconductor material, was obtained from the market and used as PM6 (trade name, manufactured by 1-material).

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

[0368]

Table 2

[0369]

Table 3

[0370]

Table 4

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

[0372]

Chemical Formula

[0373] Into a 300 mL four-necked flask, 3-Methoxythiophene (manufactured by Tokyo Chemical Industry, 5.00 g, 43.8 mmol), 2-Hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH·H2O (0.833 g, 4.38 mmol), and toluene (100 g) were charged. After purging with nitrogen, the temperature was raised to 110 °C. After stirring for 23 hours, it was cooled to room temperature. After dilution with toluene and washing twice with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: hexane = 100 wt%) to obtain 13.4 g of Compound 2 as a colorless transparent liquid. The NMR spectrum of the obtained Compound 2 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.21 (1H), 3.81 (2H), 1.77-1.71 (1H), 1.46-1.28 (m, 24H), 0.90-0.86 (m, 6H)

[0374] Compound 3 was synthesized using Compound 2.

[0375]

Chemical formula

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

[0377] Compound 4 was synthesized using Compound 3.

[0378]

Chemical formula

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

[0380] Compound 6 was synthesized using Compound 5.

[0381]

Chemical formula

[0382] Into a 50 mL four-necked flask, 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 0.477 g, 1.18 mmol), bis(pinacolato)diboron (0.752 g, 3.0 mmol), [Ir(OMe)(cod)]2 (9 mg, 0.01 mmol), and tBu-bpy (8 mg, 0.02 mmol) were charged. After purging with nitrogen, 7 g of cyclohexane was charged, and the flask was placed in an oil bath heated to 60 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. Quenching was carried out by pouring the cooled mass into water. After removing the aqueous layer from the obtained mass by liquid separation, it was dried over magnesium sulfate, filtered while passing through silica gel, and then concentrated to dryness using a rotary evaporator to obtain 0.802 g of the crude product of the target compound.

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

[0384]

Chemical Structure

[0385] Into a 100 mL four-necked flask, the crude product of Compound 6 (3.36 g), Compound 4 (5.09 g, 11.8 mmol), and THF (30.2 g) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.235 g, 0.257 mmol), P(tBu3)HBF4 (0.149 g, 0.513 mmol), and a 3 mol / L aqueous solution of K3PO4 (9.50 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. After dilution with toluene and washing twice with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: hexane / ethyl acetate = 30 / 1 (volume ratio)) to obtain 3.28 g of Compound 7 as a red viscous liquid.

[0386] Compound N-1 was synthesized using Compound 7.

[0387] [Chemical formula]

[0388] Into a 200 mL four-necked flask, compound 7 (3.28 g, 2.97 mmol), the above-mentioned compound 7-1 (2.18 g, 8.91 mmol) synthesized according to the method described in International Publication No. 2020 / 109823, p-TsOH·H2O (1.70 g, 8.91 mmol), EtOH (29.5 g), toluene (65.6 g), and MgSO4 (1.64 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 3.41 g (yield 74%) of compound N-1 as a blue-greenish black solid. For the obtained compound N-1, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.01 (2H), 8.80 (2H), 8.17 (2H), 7.74 (2H), 7.54 (2H), 4.19 (4H), 2.01-1.95 (m, 6H), 1.58-0.63 (m, 90H)

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

[0390] [Chemical formula]

[0391] Into a 300 mL four-necked flask, 3-Methoxythiophene (manufactured by Tokyo Chemical Industry, 5.00 g, 43.8 mmol), 2-Hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH·H2O (0.833 g, 4.38 mmol), and toluene (100 g) were charged. After purging with nitrogen, the temperature was raised to 110 °C. After stirring for 23 hours, it was cooled to room temperature. After diluting with toluene and separating and washing twice with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: hexane = 100 wt%) to obtain 13.4 g of Compound 9 as a colorless transparent liquid. The NMR spectrum of the obtained Compound 9 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.21 (1H), 3.81 (2H), 1.77-1.71 (1H), 1.46-1.28 (m, 24H), 0.90-0.86 (m, 6H)

[0392] Compound 10 was synthesized using Compound 9.

[0393]

Chemical Structure

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

[0395] Compound 11 was synthesized using Compound 10.

[0396]

Chemical Structure

[0397] Into a 500 mL four-necked flask, the crude form of Compound 10 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (manufactured by JiangSu GR-Chem), and THF (149 mL) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.600 g, 0.655 mmol), P(tBu3)HBF4 (0.399 g, 1.38 mmol), and an aqueous solution of 3 mol / L K3PO4 (60.6 g) were charged in this order, and then the temperature was raised to 65 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 3.72 g of Compound 11 as a yellowish-brown liquid. The NMR spectrum of the obtained Compound 11 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.08 (1H), 6.29 (1H), 4.06 (2H), 3.83 (2H), 1.85 - 1.27 (m, 34H), 0.98 - 0.86 (m, 12H)

[0398] Compound 12 was synthesized using Compound 11.

[0399]

Chemical Structure

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

[0401] Compound 14 was synthesized using Compound 13.

[0402]

Chemical Structure

[0403] Into a 50 mL four-necked flask, 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol) and THF (11.2 mL) were charged. After nitrogen substitution, the mixture was cooled to -73 °C. nBuLi (1.56 mol / L in Hexane, 1.75 mL, 2.73 mmol) was charged, and the internal temperature was maintained at -65 °C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.85 mL, 3.72 mmol) and THF (5.6 mL) were charged into a dropping funnel and slowly added dropwise to the reaction mass at an internal temperature of -65 °C. After completion of the dropwise addition, the internal temperature was maintained at -65 °C for 1 hour, then the temperature was raised to room temperature and stirred for 1 hour. Quenching was carried out by pouring 20% aqueous ammonium chloride solution (5.3 mL). After removing the aqueous layer from the obtained mass by liquid separation, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain 1.49 g of the crude product of Compound 14.

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

[0405]

Chemical Structure

[0406] A 100 mL four-necked flask was charged with the crude form of Compound 14 (1.49 g), Compound 12 (2.05 g, 3.20 mmol), and THF (29.6 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.113 g, 0.123 mmol), P(tBu3)HBF4 (0.0749 g, 0.258 mmol), and an aqueous solution of 3 mol / L K3PO4 (11.4 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 1.27 g of Compound 15 as a red liquid. The NMR spectrum of the obtained Compound 15 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.20 (1H), 7.13 - 7.10 (m, 2H), 6.93 - 6.91 (m, 1H), 4.10 (2H), 4.05 (2H), 1.93 - 0.57 (m, 80H)

[0407] Compound 16 was synthesized using Compound 15.

[0408]

Chemical Structure

[0409] Into a 50 mL four-necked flask, compound 15 (1.25 g, 1.30 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.497 g, 1.56 mmol) (manufactured by JiangSu GR-Chem), Pd(OAc)2 (0.0364 g, 0.162 mmol), [(tBu)2MePH]BF4 (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), K2CO3 (0.538 g, 3.89 mmol), and DMF (12.5 g) were charged, and nitrogen bubbling was carried out for 30 minutes. After nitrogen substitution, the internal temperature was raised to 120 °C and stirred for 5 hours. After cooling to room temperature, it was diluted with toluene, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.620 g of compound 16 as a dark red-violet liquid. The NMR spectrum of the obtained compound 16 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.74 (1H), 7.47 (2H), 7.32 (1H), 7.20 (1H), 7.12 (1H), 4.13 -4.06 (m, 6H), 1.89-0.60 (m, 95H)

[0410] Compound N-2 was synthesized using compound 16.

[0411]

Chemical Structure

[0412] Into a 50 mL four-necked flask, compound 16 (0.600 g, 0.499 mmol), compound 7-1 (0.366 g, 1.50 mmol) synthesized according to the method described in WO 2020 / 109823, p-TsOH·H2O (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), and MgSO4 (0.300 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.632 g (yield 78%) of compound N-2 as a black solid. The NMR spectrum of the obtained compound N-2 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.98-8.95 (m, 2H), 8.76-8.72 (m, 2H), 8.14-8.11 (m, 2H), 7.74 (1H), 7.50-7.32 (m, 4H), 4.19 (6H), 2.06-0.64 (m, 95H)

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

[0414]

Chemical Structure

[0415] Into a 50 mL four-necked flask, 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol), bis(pinacolato)diboron (1.58 g, 6.21 mmol), [Ir(OMe)(cod)]2 (19.8 mg, 0.0298 mmol), and tBu-bpy (16.0 mg, 0.0596 mmol) were charged. After purging with nitrogen, 15.0 g of cyclohexane was charged, and the flask was placed in an oil bath heated to 60 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The quenching was carried out by pouring the cooled mass into water. After removing the aqueous layer from the obtained mass by liquid separation, it was dried over magnesium sulfate, filtered while passing through silica gel, and then concentrated to dryness using a rotary evaporator to obtain 2.30 g of the crude product of Compound 19.

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

[0417]

Chemical formula

[0418] Into a 50 mL four-necked flask, the crude product of Compound 19 (1.13 g), Compound 12 (1.80 g, 2.81 mmol), and THF (18.2 g) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0560 g, 0.0612 mmol), P(tBu3)HBF4 (0.0372 g, 0.128 mmol), and a 3 mol / L aqueous solution of K3PO4 (5.66 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. After diluting with toluene and washing twice by liquid separation with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 1.19 g of Compound 20 as a dark red viscous liquid. The NMR spectrum of the obtained Compound 20 was analyzed. The results are as follows. 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.46 (2H), 7.20 (2H), 7.13 (2H), 4.10 (4H), 4.06 (2H), 1.94 - 0.61 (m, 126H)

[0419] Compound N-3 was synthesized using Compound 20.

[0420]

Chemical Structure

[0421] Compound 20 (1.15 g, 0.754 mmol), Compound 7-1 (0.553 g, 2.26 mmol), p-TsOH·H2O (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), and MgSO4 (0.575 g) were charged into a 100 mL four-necked flask, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.890 g (yield 60%) of Compound N-3 as a black solid. The NMR spectrum of the obtained Compound N-3 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.94 - 8.93 (m, 2H), 8.69 (2H), 8.10 (2H), 7.50 - 7.35 (m, 6H), 4.19 - 4.15 (m, 8H), 1.94 - 0.64 (m, 126H)

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

[0423]

Chemical Structure

[0424] Into a 300 mL four-necked flask, 3-Methoxythiophene (manufactured by Tokyo Chemical Industry, 4.50 g, 39.4 mmol), 2-Ethyl-1-hexanol (15.4 g, 118 mmol), p-TsOH·H2O (0.750 g, 3.94 mmol), and toluene (90 g) were charged. After purging with nitrogen, the temperature was raised to 110 °C. After stirring for 7 hours, it was cooled to room temperature. After diluting with toluene and performing liquid-liquid washing twice with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane = 100 wt%) to obtain 8.08 g of Compound 21 as a colorless transparent liquid. The NMR spectrum of the obtained Compound 21 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.22 (1H), 3.83 (2H), 1.74 - 1.64 (1H), 1.54 - 1.27 (m, 8H), 0.95 - 0.86 (m, 6H)

[0425] Compound 22 was synthesized using Compound 21.

[0426]

Chemical Structure

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

[0428] Compound 23 was synthesized using Compound 22.

[0429]

Chemical Structure

[0430] A 100 mL four-necked flask was charged with the crude product of Compound 22 (3.10 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (3.22 g, 10.1 mmol) (manufactured by JiangSu GR-Chem), and THF (31.4 mL), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.420 g, 0.458 mmol), P(tBu3)HBF4 (0.279 g, 0.962 mmol), and an aqueous solution of 3 mol / L K3PO4 (17.0 g) were charged in sequence, and then the temperature was raised to 65 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 15 / 1 (volume ratio)) to obtain 2.81 g of Compound 23 as a yellowish-brown liquid. The NMR spectrum of the obtained Compound 23 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 7.46 (1H), 7.09 (1H), 6.29 (1H), 4.06 (2H), 3.85 (2H), 1.85-1.27 (m, 18H), 0.98-0.86 (m, 12H)

[0431] Compound 24 was synthesized using Compound 23.

[0432]

Chemical Structure

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

[0434] Compound 26 was synthesized using compound 25.

[0435]

Chemical Structure

[0436] 4,8-Bis(3,5-dioctyl-2-thienyl)-2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[1,2-b:4,5-b’]dithiophene (0.956 g, 0.906 mmol), Compound 24 (1.20 g, 2.27 mmol), and THF (21.8 g) were charged into a 50 mL four-necked flask, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0415 g, 0.045 mmol), P(tBu3)HBF4 (0.0276 g, 0.095 mmol), and an aqueous solution of 3 mol / L K3PO4 (4.19 g) were charged in sequence, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 7 / 1 (volume ratio)) to obtain 0.90 g of Compound 26 as a red viscous liquid. The obtained Compound 26 was analyzed by NMR spectrum. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ9.75 (2H), 7.46 (2H), 7.40-7.39 (2H), 7.18 (2H), 6.78 (2H), 4.13-3.98 (m, 8H), 2.27 (4H), 2.45-2.37 (m, 4H), 1.85-0.70 (m, 120H)

[0437] Compound N-4 was synthesized using Compound 26.

[0438]

Chemical Structure

[0439] In a 50 mL four-necked flask, compound 26 (0.500 g, 0.294 mmol), compound 7-1 (0.215 g, 0.882 mmol), p-TsOH·H2O (0.168 g, 0.882 mmol), EtOH (4.6 g), toluene (10.0 g), and MgSO4 (0.250 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.46 g (yield 73%) of compound N-4 as a black solid. The NMR spectrum of the obtained compound N-4 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ8.93 - 8.70 (4H), 8.13 (2H), 7.53 - 7.23 (6H), 6.81 (2H), 4.14 (8H), 3.01 - 2.88 (m, 4H), 2.44 - 2.21 (m, 4H), 1.91 - 0.61 (m, 120H)

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

[0441]

Chemical formula

[0442]

Chemical formula

[0443] As the n-type semiconductor material compound N-5, SiOTIC-4F (trade name, manufactured by 1-material) was obtained from the market and used. As the n-type semiconductor material compound N-6, IEICO-4F (trade name, manufactured by 1-material) was obtained from the market and used. As the n-type semiconductor material, Compound N-7 was obtained from the market and used, which is COTIC-4F (trade name, manufactured by 1-material). As the n-type semiconductor material, Compound N-8 was obtained from the market and used, which is COTIC-4Cl (trade name, manufactured by 1-material). As the n-type semiconductor material, Compound N-9 was obtained from the market and used, which is COI-4Cl (trade name, manufactured by 1-material).

[0444] [Preparation of Ink] [Preparation of Ink (I-1)] As shown in Table 5 below, for 1,2-dimethylbenzene as the solvent, the mixture obtained by stirring Compound P-1, which is a p-type semiconductor material (polymer compound), at 60 °C for 8 hours so that its concentration is 1% by mass based on the total mass of the ink was filtered using a filter to obtain Ink (I-1).

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

[0446] [Table 5]

[0447] [Preparation of Ink (I-5)] As shown in Table 6 below, for toluene as the solvent, the mixture obtained by stirring Compound N-1, which is an n-type semiconductor material (polymer compound), at 60 °C for 8 hours so that its concentration is 1% by mass based on the total mass of the ink was filtered using a filter to obtain Ink (I-5).

[0448] [Preparation of Ink (I-6) to (I-13) and (I-36)] In the same manner as Ink (I-5), using the n-type semiconductor materials shown in Table 6, Ink (I-6) to (I-13) and (I-36) were prepared.

[0449]

Table 6

[0450] (Preparation of Ink (I-14)) As also shown in Table 7 below, for a solvent obtained by mixing chloroform, which is a solvent, and chloronaphthalene (volume ratio of 98:2), the n-type semiconductor material Compound N-1 was added at a concentration of 1% by mass based on the total mass of the ink, and the p-type semiconductor material Polymer Compound P-1 was added at a concentration of 1% by mass based on the total mass of the ink (n-type semiconductor material / p-type semiconductor material = 1 / 1). The resulting mixture was stirred at room temperature for 8 hours and then filtered using a filter to obtain Ink (I-14).

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

[0452]

Table 7

[0453] [Fabrication of PHJ Film] (Preparation Example 1) Ink (I-1) was applied onto a cleaned glass substrate by spin coating to form a coating film. After that, heat treatment was performed for 5 minutes using a hot plate heated to 70 °C under the atmosphere to dry it (pre-bake process). Then, heat treatment was performed at 100 °C for 10 minutes on the hot plate in the atmosphere (post-bake process) to form the first layer. Next, after applying ink (I-5) onto the fabricated first layer by spin coating to form a coating film, it was heat-treated for 5 minutes using a hot plate heated to 70 °C in air to dry it (pre-bake process). Then, it was heat-treated at 100 °C for 10 minutes on the hot plate in air (post-bake process) to form the second layer, and a PHJ film (active layer) was fabricated.

[0454] (Preparation Examples 2 to 23 and 49) Except for using the combinations shown in Table 8 below, in the same manner as Preparation Example 1, each of inks (I-1) to (I-13), (I-18), and (I-36) was used to prepare Preparation Examples 2 to 23 and 49, and a PHJ film (active layer) was fabricated. Note that Preparation Example 12 is a PHJ film provided with a single film of an n-type semiconductor material on a BHJ film.

[0455] [Table 8]

[0456] [Fabrication of BHJ Film] (Preparation Example 24) After applying ink (I-14) onto a cleaned glass substrate by spin coating to form a coating film, it was heat-treated for 5 minutes using a hot plate heated to 70 °C in air to dry it (pre-bake process). Then, it was heat-treated at 100 °C for 10 minutes on the hot plate in air (post-bake process) to fabricate a BHJ film.

[0457] (Preparation Examples 25 to 45 and 50) Except for using the combinations shown in Table 9 below, in the same manner as Preparation Example 24, inks (I-15) to (I-35) and (I-37) were used to prepare Preparation Examples 25 to 45 and 50, and a BHJ film was fabricated.

[0458] [Table 9]

[0459] [Fabrication of Single Film of n-Type Semiconductor Material] (Preparation Example 46) After the ink (I-5) was applied onto a cleaned glass substrate by spin coating to form a coating film, it was heat-treated for 5 minutes using a hot plate heated to 70°C in the air to dry it (pre-baking step), and then heat-treated at 100°C for 10 minutes on the hot plate in the air (post-baking step) to form a single film of the n-type semiconductor material.

[0460] (Preparation Examples 47 to 48) Preparation Examples 47 to 48 were prepared using inks (I-6) to (I-7) in the same manner as in Preparation Example 46, except for using the combinations shown in Table 10 below, and a single film of the n-type semiconductor material was formed.

[0461]

Table 10

[0462] (Manufacture of a photoelectric conversion element and its encapsulant) (Photoelectric conversion element based on Preparation Example 1 and its encapsulant) A glass substrate on which a thin film (anode) of ITO was formed with a thickness of 45 nm by sputtering was prepared, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

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

[0464] Next, a UV curable sealant as a sealing material was applied to the outer periphery of a glass substrate as a sealing substrate, and the glass substrate as a sealing substrate was bonded to the center of the glass substrate as a support substrate. Then, by irradiating with UV light, the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate to obtain a sealed body of the photoelectric conversion element. The planar shape when viewed from the thickness direction of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate was a square of 2 mm × 2 mm.

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

[0466] [Evaluation of Photoelectric Conversion Element] [Evaluation of Dark Current (Jd)] For the sealed bodies based on Preparation Examples 1 to 3 manufactured as described above, in the dark state without light irradiation, the driving of the OPD was confirmed from the shape of the IV curve measured using a known method. As shown in Table 11, the OPD could be driven in Preparation Examples 1 to 3.

[0467] [Measurement of Wavelength Band (FW90%M) that can be Detected with High Sensitivity] Using a UV-visible near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation), the light absorption spectra of the PHJ film or BHJ film on the glass substrate were measured. For the absorbance at the maximum absorption wavelength position in the absorption peak of the obtained spectrum, the wavelength range satisfying 90% or more at the absorption peak was determined as FW90%M (Full Width at 90% of the Maximum). FW90%M is a numerical value indicating the spread of a distribution that monotonically decreases around the maximum value, and is the distance (unit: nm) between the positions indicated by the values of 90% of the maximum value on both sides of the maximum value. In the present disclosure, the larger the value of FW90%M, the wider the wavelength band that can be detected with high sensitivity. In the present disclosure, the maximum value is the maximum value existing beyond 1000 nm in the light absorption spectrum. Further, when there are a plurality of maximum values in the range exceeding 1000 nm in the light absorption spectrum, the larger value of FW90%M is adopted as the value of FW90%M.

[0468] (FW90%M ratio) From the respective FW90%M values in the obtained PHJ film, BHJ film, or n-type single film, the FW90%M ratio of PHJ to BHJ or the FW90%M ratio of PHJ to n-type single film was calculated. As shown in Tables 11 and 12, in the PHJ films of Preparation Examples 1 to 12 and Preparation Example 49, the FW90%M ratio was greater than 1.00 in all cases, that is, the wavelength band that could be detected with high sensitivity was wider compared to the BHJ film or n-type single film.

[0469] (Measurement of the maximum light absorption wavelength (λmax) of the active layer) The maximum light absorption wavelength (λmax) of the active layer was measured by the method described above. As shown in Tables 11 and 12, in Preparation Examples 1 to 12 and Preparation Example 49, λmax of the active layer exceeded 1000 nm.

[0470] (Measurement of the light absorption end wavelength (λth) of the active layer) The light absorption end wavelength (λth) of the active layer was measured by the method described above.

[0471]

Table 11

[0472]

Table 12

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

[0474] As the value of the HOMO energy, the value measured by ultraviolet photoelectron spectroscopy (UPS method) was used. Ultraviolet photoelectron spectroscopy can be carried out using a photoelectron spectrometer in the atmosphere.

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

[0476] (2) Measurement of HOMO energy by UPS method For each of the obtained samples, based on the number of electrons measured by the UPS method using a photoelectron spectrometer (manufactured by RIKEN KEIKI CO., LTD., model AC-2) in the atmosphere, the HOMO energy of each of Compounds P-1 to P-4 and Compounds N-1 to N-10 was calculated. Here, the UPS method is a method of measuring the number of photoelectrons emitted with respect to the energy of ultraviolet light irradiated on the solid surface. From the minimum energy at which photoelectrons are generated, the work function can be estimated when the sample is a metal, and the HOMO energy can be estimated when the sample is a semiconductor material.

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

[0478] [Table 13]

[0479] From the above, in the present disclosure, a photoelectric conversion element and a photosensor having a wide wavelength band that can be detected with high sensitivity in the long wavelength band were obtained.

Explanation of Signs

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

Claims

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

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

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

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

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

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

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

8. The photoelectric conversion element according to claim 7, wherein n is an integer of any one of 1 to 4.

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

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

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

12. The photoelectric conversion element according to Claim 1 or Claim 2, which is a photodetection element.

13. An optical sensor including the photoelectric conversion element according to Claim 12.

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