TW202340394A - Ink composition and photoelectric conversion device using said ink composition - Google Patents

Abstract

The present invention addresses the problem of improving the characteristics of a photoelectric conversion device. The present invention pertains to an ink composition containing: a semiconductor material including at least one p-type semiconductor material and at least one n-type semiconductor material; and two or more solvents including a first solvent and a second solvent having a boiling point higher than that of the first solvent, wherein one among the p-type semiconductor material and the n-type semiconductor material is a non-fullerene compound represented by formula (I), and the polar term P(B1)(MPa0.5) of the Hansen solubility parameter of a B1-containing compound in which the terminal formed by cleaving the bond between A1 and B1 in the non-fullerene compound represented by formula (I) is terminated with a hydrogen atom, and the polar term P(S2)(MPa0.5) of the Hansen solubility parameter of the second solvent satisfy the condition represented by expression (III). (I): A1-B1-(A1)n, (III): |P(B1)-P(S2)| > 3.2(MPa0.5) (In formula (I), A1, B1, and n are as defined in the specification, and a compound in which the terminal of A1 is terminated with a hydrogen atom and a compound in which the terminal of B1 is terminated with a hydrogen atom satisfy the condition represented by expression (II). Expression (II): EHOMO(B1)-EHOMO(A1) > 2.0(eV) (In expression (II), EHOMO(B1) and EHOMO(A1) are as defined in the specification.)).

Description

Ink composition and photoelectric conversion element using the same

The present invention relates to an ink composition and a photoelectric conversion element using the same.

From the viewpoints of energy saving and carbon dioxide emission reduction, for example, photoelectric conversion elements are extremely useful devices and are attracting attention.

The photoelectric conversion element is an element including 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 side of the transparent or translucent electrode. The energy (hν) of light incident on the active layer generates charges (holes and electrons) in the active layer. The generated holes move toward the anode, and the electrons move toward the cathode. Then, the charges reaching the anode and cathode are taken out to the outside of the element.

In recent years, organic photoelectric conversion elements containing organic semiconductor materials in their active layers are being studied for various applications because they are lightweight and can easily be expanded to a large area. Furthermore, organic photoelectric conversion elements are required to further improve their characteristics. Therefore, various organic semiconductor materials have been further developed and reported. In addition, the active layer of the organic photoelectric conversion element is formed by applying an ink composition containing an organic semiconductor material and drying it. Methods are being studied to obtain high photoelectric conversion characteristics by adding additives (second solvent) to this ink composition to control the structure within the active layer. For example, in Non-Patent Document 1, it is reported that 1,8-diiodomethane (DIO) is added as the main active layer of an n-type semiconductor material using a fullerene derivative. The solvent (first solvent) has a higher boiling point than an additive that selectively dissolves fullerene derivatives, thereby improving photoelectric conversion characteristics. Furthermore, the same technology is also applied to an active layer using a non-fullerene compound (nonfullerene acceptor (NFA)) as an n-type semiconductor material (for example, see Non-Patent Document 2). [Prior art documents] [Non-patent literature]

[Non-patent document 1] "J. Am. Chem. Soc", 2008, 130, 3619-3623 [Non-patent document 2] "J. Mater. Chem. A", 2020, 8, 23628-23636

[Problem to be solved by the invention]

Non-fullerene compounds can adjust the absorption wavelength range based on molecular design. Recently, a large number of non-fullerene compounds with absorption in the near-infrared region have been reported, attracting attention as compounds that can respond to near-infrared rays. However, it is difficult to say that the characteristics required for a photoelectric conversion element, which is a photodetection element containing a non-fullerene compound, are sufficient.

Therefore, there is a demand for means that can further improve the characteristics of photoelectric conversion elements. [Means to solve the problem]

The present inventors conducted diligent research to solve the above-mentioned problems, and as a result found that the above-mentioned problems can be solved by manufacturing a photoelectric conversion element by combining predetermined solvents, and thus completed the present invention.

Therefore, the present invention provides the following [1] to [12]. [1] An ink composition, comprising: a semiconductor material, including at least one p-type semiconductor material and at least one n-type semiconductor material; and two or more solvents, including a first solvent and one having a boiling point higher than that of the first solvent. The second solvent with a high boiling point, either the p-type semiconductor material or the n-type semiconductor material is a non-fullerene compound represented by the following formula (I), and the compound containing B ¹ The polar term P (B ¹ ) (MPa ^0.5 ) of the Hansen solubility parameter of the second solvent and the polar term P (S2) (MPa ^0.5 ) of the Hansen solubility parameter of the second solvent satisfy the conditions represented by the following formula (III), so B ¹ is a terminal formed by cutting the bond between A ¹ and B ¹ in the non-fullerene compound represented by the following formula (I) and is terminated with a hydrogen atom. A ¹ -B ¹ -(A ¹ )n (I) |P(B ¹ )-P(S2)|＞3.2(MPa ^0.5 ) (III) (In formula (I), A ¹ represents an electron-withdrawing group , B ¹ represents a base containing one or more structural units and constituting a π conjugated system, n is 0 or 1, and when n is 1, the two A ^1s may be the same or different, including A ¹ A compound of A ¹ whose terminal is terminated with a hydrogen atom formed by cleaving the bond with B ¹ and a compound containing B ¹ satisfy the conditions represented by the following formula (II); E _HOMO (B ¹ )-E _HOMO (A ¹ )>2.0 (eV) (II) (In formula (II), E _HOMO (B ¹ ) (eV) represents a compound containing B ¹ whose terminal is terminated with a hydrogen atom, formed by cutting the bond between A ¹ and B ¹ The value of the energy level of the highest occupied orbital, E _HOMO (A ¹ ) (eV) represents the highest occupied orbital of a compound containing A ¹ formed by cutting the bond between A ¹ and B ¹ and terminated with a hydrogen atom. The value of the energy level.)) [2] The ink composition according to [1], wherein the second solvent is a solvent having a boiling point that is 30° C. or more higher than the boiling point of the first solvent. [3] The ink composition according to [1] or [2], wherein the second solvent is an ether solvent, an aromatic hydrocarbon solvent, a ketone solvent, or an ester solvent. [4] The ink composition according to any one of [1] to [3], wherein the non-fullerene compound represented by the formula (I) is an n-type semiconductor material. [5] The ink composition according to any one of [1] to [4], wherein in the formula (I), at least one of the one or more structural units contained in ^B1 The first structural unit is a structural unit represented by the following formula (IV), and the remaining second structural units other than the first structural unit are a divalent group containing an unsaturated bond, or a divalent aromatic carbocyclic group Or a divalent aromatic heterocyclic group. When there are two or more first structural units, the two or more first structural units may be the same or different. When there are two or more second structural units. In the case of , there are two or more second structural units which may be the same or different. [Chemical 1] (In formula (IV), Ar ¹ and Ar ² each independently represent an aromatic carbocyclic ring that may have a substituent or an aromatic heterocyclic ring that may have a substituent, and Y represents a direct bond, -C(=O)- represents a group or oxygen atom, R independently represents: 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 alkyl group that may have a substituent baseoxy group, optionally substituted cycloalkyloxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted cycloalkylthio group, optionally substituted aryloxy group Thio group, monovalent heterocyclic group which may have a substituent, substituted amine group which may have a substituent, acyl group which may have a substituent, imine residue which may have a substituent, amide group which may have a substituent, amide group which may have a substituent, substituted oxycarbonyl which may have a substituent, alkenyl which may have a substituent, cycloalkenyl which may have a substituent, alkynyl which may have a substituent, alkynyl which may have a substituent A cycloalkynyl group, a cyano group, a nitro group, a group represented by -C(=O)-R ^a , or a group represented by -SO ₂ -R ^b , R ^a and R ^b each independently represent: a hydrogen atom, which can be An alkyl group having a substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, an aryloxy group that may have a substituent, or a monovalent heterocyclic group that may have a substituent; there are multiple R's may be the same or different from each other) [6] The ink composition according to [5], wherein the first structural unit is a structural unit represented by the following formula (V). [Chemicalization 2] (In formula (V), Y and R are as defined above, X ¹ and X ² each independently represent a sulfur atom or an oxygen atom, and Z ¹ and Z ² each independently represent a group represented by =C(R)- or nitrogen atom) [7] The ink composition according to [6], wherein the first structural unit is a structural unit represented by the following formula (V-1). [Chemical 3] (In formula (V-1), Y represents a group represented by -C(=O)- or an oxygen atom, and R each independently represents: a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkyl group that may have a substituent a cycloalkyl group, 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 alkyl group that may have a substituent Thio group, cycloalkylthio group which may have a substituent, arylthio group which may have a substituent, monovalent heterocyclic group which may have a substituent, substituted amino group which may have a substituent, acyl group which may have a substituent, imine residue which may have a substituent, amide group which may have a substituent, amide group which may have a substituent, substituted oxycarbonyl group which may have a substituent, alkenyl group which may have a substituent, which may have a substituent a cycloalkenyl group, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, a nitro group, a group represented by -C(=O)-R ^a , or -SO ₂ -R ^b The represented groups, R ^a and R ^b each independently represent: a hydrogen 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 aryl group which may have a substituent. oxygen group, or a monovalent heterocyclic group which may have a substituent; the plural R present may be the same or different) [8] The ink composition as described in [6] or [7], wherein B ¹ is A divalent group selected from the group consisting of structures represented by the following formula (VII-1) to formula (VII-16). -CU1- (VII-1) -CU1-CU1- (VII-2) -CU1-CU2- (VII-3) -CU1-CU1-CU1- (VII-4) -CU1-CU2-CU1- (VII- 5) -CU1-CU1-CU2- (VII-6) -CU1-CU2-CU2- (VII-7) -CU2-CU1-CU2- (VII-8) -CU1-CU1-CU1-CU1- (VII- 9) -CU1-CU1-CU1-CU2- (VII-10) -CU1-CU1-CU2-CU1- (VII-11) -CU1-CU1-CU2-CU2- (VII-12) -CU1-CU2-CU1 -CU2- (VII-13) -CU1-CU2-CU2-CU1- (VII-14) -CU1-CU2-CU2-CU2- (VII-15) -CU2-CU1-CU2-CU2- (VII-16) (In Formula (VII-1) to Formula (VII-16), CU1 represents the first structural unit, and CU2 represents the second structural unit; when there are two or more CU1s, there are two or more CU1s. They may be the same or different. When there are two or more CU2s, the two or more CU2s may be the same or different.) [9] The ink composition according to any one of [1] to [8], Wherein, the p-type semiconductor material is a conjugated polymer compound. [10] A cured film obtained by curing the ink composition according to any one of [1] to [9]. [11] A photoelectric conversion element including a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, the active layer being the cured film according to [10]. [12] The photoelectric conversion element according to [11] is a photodetection element. [Effects of the invention]

According to the present invention, it is possible to provide a photoelectric conversion element in which characteristics are further improved by using a predetermined solvent in combination with a method for manufacturing the photoelectric conversion element.

Hereinafter, embodiments of the present invention will be described, and in particular, photoelectric conversion elements will be described with reference to the drawings. In addition, the drawings only schematically show the shapes, sizes, and arrangements of the constituent elements to an extent that allows the invention to be understood. The present invention is not limited to the following description, and each constituent element can be appropriately changed within the scope of the spirit of the present invention. In addition, the structure of the embodiment of the present invention is not necessarily limited to manufacturing or using the configuration shown in the drawings.

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

The term "non-fullerene compound" refers to a compound that is neither fullerene nor fullerene derivatives.

The so-called "π conjugated system" refers to a system in which π electrons exist non-locally on multiple bonds.

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. In addition, the total amount of structural units contained in the polymer compound is 100 mol%.

The "structural unit" means that the compound and polymer compound of this embodiment have one or more residues derived from the raw material compound (monomer).

"Hydrogen atom" can be a light hydrogen atom or a heavy hydrogen atom.

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

The form of "may have a substituent" includes two forms: a case in which all the hydrogen atoms constituting the compound or group are unsubstituted, and a case in which one or more hydrogen atoms are partially or entirely substituted with a substituent.

Examples of "substituent" include: halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, alkyloxy group, cycloalkyloxy group, alkylthio group, Cycloalkylthio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, substituted amine group, acyl group, imine residue, amide group, amide imine group, substituted oxycarbonyl group, cyanide group, alkylsulfonyl group, and nitro group. Furthermore, when the number of carbon atoms is mentioned in this specification, the number of carbon atoms generally does not include the number of carbon atoms of the substituent.

In this specification, unless otherwise specified, the "alkyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkyl group does not include the number of carbon atoms of the substituent, and is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20. The number of carbon atoms of the branched or cyclic alkyl group does not include the number of carbon atoms of the substituent, and is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.

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

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 alkyl group described above is substituted by a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

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

"Cycloalkyl" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms of the cycloalkyl group does not include the number of carbon atoms of the substituent, and is usually 3 to 30, preferably 12 to 19.

Examples of the cycloalkyl group include unsubstituted alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl, and hydrogen atoms in these groups are substituted by alkyl groups, alkyloxy groups, A group substituted by substituents such as aryl groups and fluorine atoms.

Specific examples of the cycloalkyl group having a substituent include methylcyclohexyl and ethylcyclohexyl.

The "p-valent aromatic carbocyclic group" (p represents an integer of 1 or more) refers to an atomic group remaining after removing p hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent. The p-valent aromatic carbocyclic group may further have a substituent. In addition, "aromatic carbocyclic ring" includes a structure in which two or more carbocyclic rings (aromatic rings) are spanned by, for example, a heteroatom-containing group (substituent).

"Aryl group" is a monovalent aromatic carbocyclic group, and refers to an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring from an aromatic hydrocarbon which may have a substituent.

The aryl group may have a substituent. Specific examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2-pyrenyl, 4- Pyrenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl and the hydrogen atoms in these groups are replaced by alkyl, A group substituted by substituents such as alkyloxy groups, aryl groups, and fluorine atoms.

The "alkyloxy group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkyloxy group does not include the number of carbon atoms of the substituent, and is usually 1 to 40, preferably 1 to 10. The number of carbon atoms of the branched or cyclic alkyloxy group does not include the number of carbon atoms of the substituent, and is usually 3 to 40, preferably 4 to 10.

The alkyloxy group may have a substituent. Specific examples of the alkyloxy group include: methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, and tert-butyloxy group , n-pentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3 , 7-dimethyloctyloxy, 3-heptyldodecyloxy, lauryloxy and hydrogen atoms in these groups are substituted by alkyloxy, aryl, fluorine atoms, etc. base.

The cycloalkyl group contained in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms of the cycloalkyloxy group does not include the number of carbon atoms of the substituent, and is usually 3 to 30, preferably 12 to 19.

Examples of the cycloalkyloxy group include unsubstituted cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy, and hydrogen atoms in these groups are replaced by fluorine atoms. , alkyl and other substituted groups.

The number of carbon atoms of the "aryloxy group" does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48.

The aryloxy group may have a substituent. Specific examples of the aryloxy group include: phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, and 1-pyrenyloxy group , and groups in which the hydrogen atoms in these groups are substituted by substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.

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

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

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

Examples of the cycloalkylthio group which may have a substituent include a cyclohexylthio group.

The number of carbon atoms of the "arylthio group" does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48.

The arylthio group may have a substituent. Examples of the arylthio group include: phenylthio group, C1 to C12 alkyloxyphenylthio group (C1 to C12 indicates that the number of carbon atoms of the group described next is 1 to 12. The same applies below), C1～C12 alkylphenylthio, 1-naphthylthio, 2-naphthylthio and pentafluorophenylthio.

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

The p-valent heterocyclic group may further have a substituent. The number of carbon atoms of the p-valent heterocyclic group does not include the number of carbon atoms of the substituent, and is usually 2 to 30, preferably 2 to 6.

Examples of substituents that the heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, and a substituted amine. group, acyl group, imine residue, amide group, amide imine group, substituted oxycarbonyl group, alkenyl group, alkynyl group, cyano group and nitro group. The p-valent heterocyclic group includes "p-valent aromatic heterocyclic group".

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

Aromatic heterocyclic compounds include, in addition to compounds in which the heterocycle itself exhibits aromaticity, compounds in which the heterocycle itself does not exhibit aromaticity but has an aromatic ring condensed into the heterocycle.

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

Among the aromatic heterocyclic compounds, specific examples of compounds in which the aromatic heterocyclic ring itself does not exhibit aromaticity but has an aromatic ring condensed on the heterocyclic ring include: phenoxazine, phenylthiazine, and dibenzoboron. Heterocyclopentadiene, dibenzosilole and benzopyran.

The number of carbon atoms of the monovalent heterocyclic group does not include the number of carbon atoms of the substituent, and is usually 2 to 60, preferably 4 to 20.

The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include: thienyl, pyrrolyl, furyl, pyridyl, piperidyl, quinolyl, isoquinolyl, and pyrimidine groups, triazinyl groups, and groups in which the hydrogen atoms in these groups are substituted by alkyl groups, alkyloxy groups, etc.

"Substituted amine group" means an amine group having a substituent. Examples of the substituent of the amino group include an alkyl group, an aryl group and a monovalent heterocyclic group, and an alkyl group, an aryl group or a monovalent heterocyclic group is preferred. The number of carbon atoms of the substituted amino group is usually 2 to 30.

Examples of the substituted amino group include dialkylamino groups such as dimethylamino group and diethylamino group; diphenylamino group, bis(4-methylphenyl)amine group, bis(4- Diarylamine groups such as tertiary butylphenyl)amine group and bis(3,5-di-tertiary butylphenyl)amine group.

The "acyl group" may have a substituent. The number of carbon atoms of the acyl group does not include the number of carbon atoms of the substituent, and is usually 2 to 20, preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propyl group, a butyl group, an isobutyl group, a trimethylacetyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

The so-called "imine residue" refers to the atomic group remaining after removing a hydrogen atom directly bonded to a carbon atom or a nitrogen atom constituting a carbon atom-nitrogen atom double bond from an imine compound. The so-called "imine compound" refers to an organic compound with a carbon atom-nitrogen atom double bond in the molecule. Examples of the imine compound include aldimines, ketimines, and aldimines in which a hydrogen atom bonded to a nitrogen atom constituting a carbon atom-nitrogen atom double bond is substituted with an alkyl group or the like.

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

[Chemical 4]

"Camide group" refers to the atomic group remaining after removing a hydrogen atom bonded to a nitrogen atom from amide. The number of carbon atoms of the amide group is usually 1 to 20, preferably 1 to 18. Specific examples of the amide group include a formamide group, an acetamide group, a propionamide group, a butylamide group, a benzamide group, a trifluoroacetamide group, and a pentafluorobenzamide group. base, dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, diphenylamide group, di-trifluoroacetamide group, and di-pentafluorobenzamide group Amino group.

The so-called "acyl imine group" refers to the atomic group remaining after removing a hydrogen atom bonded to a nitrogen atom from the acyl imine. The number of carbon atoms of the amide group is usually 4 to 20. Specific examples of the acyl imine group include groups represented by the following structural formulas.

[Chemistry 5]

The "substituted oxycarbonyl group" refers to a group represented by R'-O-(C=O)-. Here, R' represents an alkyl group, an aryl group, an aralkyl group, or a monovalent heterocyclic group.

The number of carbon atoms of the substituted oxycarbonyl group does not include the number of carbon atoms of the substituent, and is usually 2 to 60, preferably 2 to 48.

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

The "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkenyl group does not include the number of carbon atoms of the substituent, and is usually 2 to 30, preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkenyl group does not include the number of carbon atoms of the substituent, and is usually 3 to 30, preferably 4 to 20.

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

"Cycloalkenyl" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group does not include the number of carbon atoms of the substituent, and is usually 3 to 30, preferably 12 to 19.

Examples of the cycloalkenyl group include unsubstituted cycloalkenyl groups such as cyclohexenyl groups, and those in which hydrogen atoms in these groups are substituted by alkyl groups, alkyloxy groups, aryl groups, or fluorine atoms. base.

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

The "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkenyl group does not include the number of carbon atoms of the substituent, and is usually 2 to 20, preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkenyl group does not include the number of carbon atoms of the substituent, and is usually 4 to 30, preferably 4 to 20.

The alkynyl group may have a substituent. Specific examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1- Hexynyl group, 5-hexynyl group, and groups in which hydrogen atoms in these groups are substituted by alkyloxy groups, aryl groups, or fluorine atoms.

"Cycloalkynyl" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms of the cycloalkynyl group does not include the number of carbon atoms of the substituent, and is usually 4 to 30, preferably 12 to 19.

Examples of cycloalkynyl groups include unsubstituted cycloalkynyl groups such as cyclohexynyl groups, and groups in which hydrogen atoms in these groups are substituted by alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. .

Examples of the cycloalkynyl group having a substituent include methylcyclohexynyl and ethylcyclohexynyl.

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

The symbol "*" that can be marked in the chemical formula indicates a bond.

"Ink composition (hereinafter, sometimes referred to as ink)" refers to a liquid used in the coating method and is not limited to a colored liquid. In addition, "coating method" includes methods that use liquid substances to form films (layers). Examples include: slot die coating method, slit coating method, blade coating method, spin coating method, casting method, micro-coating method, etc. Gravure coating method, gravure coating method, rod coating method, roller coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, gravure printing method, flexographic printing method, lithographic printing method , inkjet printing method, dispenser printing method, nozzle coating method and capillary coating method.

The ink composition may be a solution or a dispersion such as a dispersion, emulsion (emulsion), or suspension (suspension).

The "absorption peak wavelength" is a parameter determined based on the absorption peak of the absorption spectrum measured within a predetermined wavelength range, and refers to the wavelength of the absorption peak with the maximum absorbance among the absorption peaks of the absorption spectrum.

The so-called "External Quantum Efficiency" is also called EQE (External Quantum Efficiency), and refers to the number of generated electrons that can be taken out to the outside of the photoelectric conversion element relative to the number of photons irradiated onto the photoelectric conversion element. , a value expressed as a ratio (%).

The ink composition of this embodiment is the following ink composition, which includes: semiconductor materials, including at least one p-type semiconductor material and at least one n-type semiconductor material; and two or more solvents, including the first solvent and the above-mentioned A second solvent with a higher boiling point than the first solvent, and either the p-type semiconductor material or the n-type semiconductor material is a non-fullerene compound represented by the following formula (I), including The polar term P (B ¹ ) (MPa ^0.5 ) of the Hansen solubility parameter of the compound B ¹ and the polar term P (S2) (MPa ^0.5 ) of the Hansen solubility parameter of the second solvent satisfy the following formula (III) According to the conditions shown, the terminal B ¹ formed by cutting the bond between B ¹ and A ¹ in the non-fullerene compound represented by the following formula (I) is terminated with a hydrogen atom. A ¹ -B ¹ -(A ¹ )n (I) |P(B ¹ )-P(S2)|＞3.2(MPa ^0.5 ) (III) (In formula (I), A ¹ represents an electron-withdrawing group , B ¹ represents a base containing one or more structural units and constituting a π conjugated system, n is 0 or 1, and when n is 1, the two A ^1s may be the same or different, including A ¹ A compound of A ¹ whose terminal is terminated with a hydrogen atom formed by cleaving the bond with B ¹ and a compound containing B ¹ satisfy the conditions represented by the following formula (II); E _HOMO (B ¹ )-E _HOMO (A ¹ )>2.0 (eV) (II) (In formula (II), E _HOMO (B ¹ ) (eV) represents a compound containing B ¹ whose terminal is terminated with a hydrogen atom, formed by cutting the bond between B ¹ and A ¹ (Hereinafter, sometimes simply referred to as a compound containing B ¹ ) The value of the energy level of the highest occupied orbital, E _HOMO (A ¹ ) (eV), represents the terminal utilization formed by cutting the bond between A ¹ and B ¹ The value of the energy level of the highest occupied orbit of a compound of A ¹ terminated by a hydrogen atom (hereinafter sometimes referred to as a compound containing A ¹ )))

Hereinafter, compounds as semiconductor materials that can be included in the ink composition of this embodiment will be described in detail.

1.Non-fullerene compounds First, compounds usable as semiconductor materials in the ink composition of this embodiment will be described. The non-fullerene compound of this embodiment can be suitably used as an n-type semiconductor material of a photoelectric conversion element, especially an active layer.

Furthermore, as already explained, whether the non-fullerene compound functions as a p-type semiconductor material or an n-type semiconductor material in the active layer depends on the highest occupied orbital (highest occupied molecular orbital) of the selected compound. The value of the energy level of the domain (Highest Occupied Molecular Orbital, HOMO) or the value of the energy level of the lowest unoccupied orbital (Lowest Unoccupied Molecular Orbital (LUMO)) is relatively determined.

The relationship between the HOMO and LUMO energy level values of the p-type semiconductor material and the HOMO and LUMO energy level values of the n-type semiconductor material contained in the active layer can be appropriately set so that the photoelectric conversion element (photodetection element) can function range of functions.

The non-fullerene compound of this embodiment is a compound represented by the following formula (I). A ¹ -B ¹ - (A ¹ )n (I)

In the formula (I), A ¹ represents an electron-withdrawing group, and B ¹ represents a group containing one or more structural units and constituting a π conjugated system. n is 0 or 1. When n is 1, there are two Each A ¹ may be the same or different, and the compound containing A ¹ whose terminal is terminated with a hydrogen atom formed by cutting the bond between A ¹ and B ¹ satisfies the following formula ( ^II ) represented by the compound containing B 1 condition. E _HOMO (B ¹ )-E _HOMO (A ¹ )>2.0 (eV) (II)

In the formula (II), E _HOMO (B ¹ ) (eV) represents the value of the energy level of the highest occupied orbital of a compound containing B ¹ whose terminal is terminated with a hydrogen atom and is formed by cutting the bond between B ¹ and A ¹ , E _HOMO (A ¹ ) (eV) represents the value of the energy level of the highest occupied orbital of a compound containing A ¹ whose terminal is terminated with a hydrogen atom, which is formed by cutting the bond between B ¹ and A ¹ .

The non-fullerene compound of this embodiment is a non-fullerene compound represented by the formula (I), and is composed of A ¹ which is an electron-withdrawing monovalent group and B ¹ which is a monovalent group or a divalent group. A compound formed by bonding at one or both ends.

In the non-fullerene compound of this embodiment, it is preferable that not only B ¹ but also A ¹ be included in the entire non-fullerene compound to form a π conjugated system.

Among the non-fullerene compounds represented by the formula (I) in this embodiment, the compound containing A ¹ and the compound containing B ¹ satisfy the conditions represented by the formula (II). In other words, the non-fullerene compound represented by the formula (I) is configured such that the energy level value (E _HOMO (B ¹ )) of the highest occupied orbital (HOMO) of the compound containing B ¹ is equal to the value of the energy level of the compound containing A ¹ The difference in the value of the energy level of the highest occupied orbital (HOMO) (E _HOMO (A ¹ )) is greater than 2.0 eV.

In the non-fullerene compound of this embodiment, the value of the energy level of the highest occupied orbital of the compound containing B ¹ (E _HOMO (B ¹ )) and the energy level of the highest occupied orbital of the compound containing A ¹ are The difference in value (E _HOMO (A ¹ )) can increase the charge shift in the ground state and can produce strong interactions between molecules. Therefore, from the perspective of improving charge transport and further improving EQE, it is relatively Preferably, it is greater than 2.0 eV, and more preferably, it is greater than 2.2 eV.

The value of the energy level of the highest occupied orbital (HOMO) can be calculated using any previously known suitable computational science method, such as Gaussian 16, a quantum chemical calculation program produced by Gaussian Company. Specifically, for a compound in which the terminal of B ¹ is terminated with a hydrogen atom and/or a compound in which the terminal of A ¹ is terminated with a hydrogen atom, the above-mentioned quantum chemical calculation program can be used and the density functional method at the B3LYP level can be used. For structural optimization, the value calculated using 6-31G as the basis function was set to the value of the energy level of the highest occupied orbital (unit: eV).

In the formula (I), when n is 1 and there are two A ^1's that are different from each other, two compounds in which the terminals generated by cutting out two A ^1's are terminated with hydrogen atoms can be used. The average value of the energy levels of the highest occupied orbitals is set to the value of the highest occupied orbital energy of the compound containing A ¹ .

Calculation examples of E _HOMO (A ¹ ) and E _HOMO (B ¹ ) are shown in the following Tables 1 to 3.

[Table 1] (Table 1) Compounds containing A ¹ E _HOMO (A ¹ ) [eV] -7.61 -7.20 -7.62 -7.32

[Table 2] (Table 2) Compounds containing B ¹ E _HOMO (B ¹ ) [eV] -4.77 -4.93 -4.41 -4.97 -4.98

[Table 3] (Table 3) Compounds containing B ¹ E _HOMO (B ¹ ) [eV] -4.63 -4.77 -4.68 -4.80

Hereinafter, A ¹ and B ¹ that can constitute the non-fullerene compound of this embodiment, and specific examples of the non-fullerene compound will be described.

(1) About A ¹ In the non-fullerene compound of this embodiment, A ¹ is an electron-withdrawing monovalent group. When there are two A ¹ 's, the two A ^1's may be the same or different. From the viewpoint of making the synthesis of the non-fullerene compound easier, the two A ¹ 's present are preferably the same group.

Examples of A ¹ include groups represented by -CH=C(-CN) ₂ and groups represented by the following formulas (a-1) to formula (a-9).

[Chemical 6]

In formula (a-1) to formula (a-7), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. Carbocyclic and heterocyclic rings may be single rings or condensed rings. When the rings have multiple substituents, the multiple substituents may be the same or different.

Examples of the carbocyclic ring represented by T which may have a substituent include an aromatic carbocyclic ring, and an aromatic carbocyclic ring is preferred. Specific examples of the optionally substituted carbocyclic ring represented by T include benzene ring, naphthalene ring, anthracene ring, condensed tetraphenyl ring, condensed pentaphenyl ring, pyrene ring and phenanthrene ring, preferably benzene ring, naphthalene ring ring and phenanthrene ring, more preferably benzene ring and naphthalene ring, still more preferably benzene ring. These rings may have substituents.

Examples of the heterocyclic ring represented by T which may have a substituent include an aromatic heterocyclic ring, and an aromatic carbocyclic ring is preferred. Specific examples of the optionally substituted heterocyclic ring represented by T include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, and a thiazole ring. and thienothiophene ring, preferably thiophene ring and pyridine ring, pyrazine ring, thiazole ring and thienothiophene ring, more preferably thiophene ring. These rings may have substituents.

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

X ⁴ _{, X} ^{5 and} the basis represented.

X ⁷ represents a hydrogen atom or a halogen atom, a cyano group, an alkyl group which may have a substituent, an alkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group. X ⁷ is preferably cyano group.

R ^a1 , R ^a2 , R ^a3 , R ^a4 and R ^a5 each independently represent a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, an alkyloxy group which may have a substituent, an aryl group which may have a substituent, or The monovalent heterocyclic group is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.

[Chemical 7]

In formula (a-8) and formula (a-9), R ^a6 and R ^a7 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a cycloalkyl group which may have a substituent. An alkyloxy group with a substituent, a cycloalkyloxy group that may have a substituent, a monovalent aromatic carbocyclic group that may have a substituent, or a monovalent aromatic heterocyclic group that may have a substituent, there are multiple R ^a6 and R ^a7 may be the same as or different from each other.

Specific examples of the electron-withdrawing monovalent group represented by A ¹ include the following formulas (a-1-1) to formula (a-1-4), and formula (a-5-1) and formula (a-6-1), the group represented by formula (a-6-2) and formula (a-7-1).

[Chemical 8]

Formula (a-1-1) to Formula (a-1-4), and Formula (a-5-1), Formula (a-6-1), Formula (a-6-2) and Formula (a- In 7-1), the plurality of R ^a10 each independently represents a hydrogen atom or a substituent, and R ^a1 , R ^a2 , R ^a3 , R ^a4 , and R ^a5 each independently have the same meaning as above.

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

It is preferred that A ¹ and A ² each independently include one or more electron-withdrawing groups selected from the group consisting of a cyano group, a carbonyl group and a thiocarbonyl group.

Preferred examples of the electron-withdrawing monovalent group represented by A ¹ include groups represented by the following formula.

[Chemical 9]

[Chemical 10]

(2) Regarding B ¹ specifically, B ¹ is a group including one or more pairs of atoms that are π-bonded to each other, and a π electron cloud is spread throughout B ¹ .

B ¹ preferably has a structure represented by the following formula. [Chemical 11]

In the formula, Ar ^a , Ar ^b and Ar ^c each independently represent an aromatic carbocyclic ring which may have substituents and may contain multiple ring structures, and the multiple ring structures may be condensed, or may have substituents and may contain An aromatic heterocycle with multiple ring structures and multiple ring structures that can be ring-condensed. Ar ^d and Ar ^e each independently represent an aromatic heterocycle that may have a substituent, may contain multiple ring structures, and the multiple ring structures can be ring-condensed. A valent aromatic carbocyclic group or a divalent aromatic heterocyclic group that may have a substituent, may include multiple ring structures, and the multiple ring structures may be condensed, in A ^a , Ar ^b , ^Arc , Ar ^d and Ar When there are multiple ^e respectively, the multiple A ^a , Ar ^b , ^Arc , Ar ^d and A ^e may be the same or different respectively. x, y and z are 0, 1, 2 or 3, and i is 0, 1, 2 or 3, k is 0 or an integer from 1 to 10, m is 0 or an integer from 1 to 10.

More specifically, B ¹ is preferably a monovalent group or a divalent group that contains one or more structural units and constitutes a π conjugated system. Here, B ¹ as a monovalent group refers to a group in which one of the ends of B ¹ as a divalent group is terminated with a hydrogen atom.

The first structural unit (hereinafter also referred to as the first structural unit CU1) that is at least one of the one or more structural units included in B ¹ is preferably a structural unit represented by the following formula (IV), and the first structural unit is preferably represented by the following formula (IV). The remaining second structural unit (hereinafter, also referred to as the second structural unit CU2) other than the first structural unit is preferably a divalent group containing an unsaturated bond, a divalent aromatic carbocyclic group or a divalent aromatic heterocyclic group. base.

In formula (I), when there are two or more first structural units, the two or more first structural units may be the same or different. When there are two or more second structural units, there are two The above second structural units may be the same or different.

[Chemical 12]

In the formula (IV), Ar ¹ and Ar ² each independently represent an aromatic carbocyclic ring that may have a substituent or an aromatic heterocyclic ring that may have a substituent, Y represents a direct bond, and -C(=O)- represents of a group or an oxygen atom, R independently represents: 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 alkyl group that may have a substituent Oxy group, optionally substituted cycloalkyloxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted cycloalkylthio group, optionally substituted arylthio group group, a monovalent heterocyclic group that may have a substituent, a substituted amine group that may have a substituent, a acyl group that may have a substituent, an imine residue that may have a substituent, a amide group that may have a substituent, amide group having a substituent, a substituted oxycarbonyl group that may have a substituent, an alkenyl group that may have a substituent, a cycloalkenyl group that may have a substituent, an alkynyl group that may have a substituent, a ring that may have a substituent Alkynyl group, cyano group, nitro group, a group represented by -C(=O)-R ^a , or a group represented by -SO ₂ -R ^b , R ^a and R ^b each independently represent: a hydrogen atom, which may have 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, or a monovalent heterocyclic group which may have a substituent. Multiple R's may be the same or different from each other.

In the formula (IV), the aromatic carbocyclic ring constituting Ar ¹ and Ar ² is preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have substituents.

The aromatic heterocycles that can constitute Ar ¹ and Ar ² are preferably oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, thienothiophene ring, benzothiophene ring, pyrrole ring, phosphatide ring Cyclopentadiene ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophospholane ring, as well as phenoxazine ring, phenthiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring. These rings may have substituents.

The halogen atom represented by R is preferably a fluorine atom.

The alkyl group which may have a substituent represented by R is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 15 carbon atoms which may have a substituent, and still more preferably An alkyl group having 1 to 12 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent.

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

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

The optionally substituted aryl group represented by R is preferably an optionally substituted aryl group having 6 to 15 carbon atoms, more preferably an optionally substituted phenyl group or naphthyl group.

The substituent that the aryl group represented by R may have is preferably a halogen atom (for example, a chlorine atom, a fluorine atom), an alkyl group having 1 to 12 carbon atoms (for example, a methyl group, a trifluoromethyl group, a tert-butyl group, an octyl group, or a halogen atom). group, dodecyl), alkyloxy group with 1 to 12 carbon atoms (such as methoxy, ethoxy, octyloxy), alkylsulfonyl group with 1 to 12 carbon atoms (such as ten dialkyl sulfonyl group), and/or cyano group.

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

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

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

The optionally substituted alkylthio group represented by R is preferably an optionally substituted alkylthio group having 1 to 6 carbon atoms, more preferably an optionally substituted alkylthio group having 1 to 3 carbon atoms, More preferably, it is a methylthio group or a propylthio group which may have a substituent.

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

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

The optionally substituted monovalent heterocyclic group represented by R is preferably a 5- or 6-membered monovalent heterocyclic group that may have a substituent. Examples of the 5-membered monovalent heterocyclic group include: thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, and pyrrole alkylinyl. Examples of the 6-membered monovalent heterocyclic group include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, piperidinyl, piperazinyl, morpholinyl, and tetrahydropyranyl.

The monovalent heterocyclic group represented by R which may have a substituent is more preferably a thienyl, furyl, thiazolyl, oxazolyl, pyridyl or pyrazinyl group, and these groups may have a substituent.

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

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

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

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

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

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

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

The plurality of R's are each independently preferably an alkyl group which may have a substituent, more preferably an alkyl group having 1 to 15 carbon atoms which may have a substituent, further preferably an alkyl group having 1 to 15 carbon atoms which may have a substituent. 12 alkyl groups, and more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent. Particularly preferably, the plurality of R present are all alkyl groups having 1 to 10 carbon atoms which may have a substituent.

Among the group represented by -C(=O)-R ^a represented by R and the group represented by -SO ₂ -R ^b , R ^a is preferably a hydrogen atom, and R ^b is preferably an alkane which may have a substituent. group or an alkyloxy group which may have a substituent, more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an alkyloxy group having 1 to 12 carbon atoms which may have a substituent, still more preferably An alkyl group having 1 to 12 carbon atoms which may have a substituent or an alkyloxy group having 1 to 6 carbon atoms which may have a substituent, more preferably methyl, ethyl, 2-methylpropyl, octyl group, dodecyl, or ethoxy group, and these groups may have substituents.

Examples of the structural unit represented by formula (IV) include structural units represented by the following formula.

[Chemical 13]

[Chemical 14]

[Chemical 15]

In the above formula, R is as already explained.

The structural unit represented by the formula (IV) that can constitute B ¹ is preferably a structural unit represented by the following formula (V).

[Chemical 16]

In formula (V), Y and R are as already explained. X ¹ and X ² each independently represent a sulfur atom or an oxygen atom, and Z ¹ and Z ² each independently represent a group represented by =C(R)- or a nitrogen atom.

Examples of the structural unit represented by formula (V) include structural units represented by the following formula.

[Chemical 17]

The structural unit represented by the formula (V) that can constitute ^B1 is preferably a divalent polycyclic condensed ring group that may have a substituent and contains two or more thiophene rings and an sp3 carbon atom as a structural element as follows: The structural unit represented by formula (V-1).

[Chemical 18]

In formula (V-1), Y and R are as defined above.

Preferable specific examples of the structural unit represented by the formula (V-1) include structural units represented by the following formula.

[Chemical 19]

Examples of suitable structural units represented by formula (V) that can constitute B ¹ include structural units represented by the following formula (V-2).

[Chemistry 20]

In the formula (V-2), X ¹ and X ² , Z ¹ and Z ² and R are as described above.

Examples of the structural unit represented by formula (V-2) include structural units represented by the following formulas (V-2-1) to formula (V-2-16).

[Chemistry 21]

Preferable specific examples of the structural unit represented by formula (V-2) include structural units represented by the following formula.

[Chemistry 22]

In this embodiment, B ¹ preferably includes a first structural unit (first structural unit CU1 ) represented by the formula (IV) or formula (V).

Examples of the second structural unit (second structural unit CU2) that B ¹ may include other than the structural unit represented by the formula (IV) or formula (V) include: a divalent group containing an unsaturated bond, a divalent group valent aromatic carbocyclic groups and divalent aromatic heterocyclic groups.

The "bivalent group containing an unsaturated bond" as the second structural unit CU2 is, for example, a group represented by -(CR=CR)n- (R is as defined above, n is an integer greater than or equal to 1; the value of n is smaller than Preferably it is 1 or 2, more preferably 1), a group represented by -C≡C-, and a phenylene group.

Specific examples of the "divalent group containing an unsaturated bond" include: ethylene-1,2-diyl, 1,3-butadiene-1,4-diyl, and acetylene-1,2-diyl. , and phenyl.

Specific examples of the "bivalent aromatic heterocyclic group" of the second structural unit CU2 include groups represented by the following formulas (101) to (191). These groups may further have substituents.

[Chemistry 23]

[Chemistry 24]

[Chemical 25]

[Chemical 26]

In Formula (101) to Formula (191), R has the same meaning as above.

Specific examples of the "bivalent aromatic carbocyclic group" of the second structural unit CU2 include: phenylene group (for example, the following formula 1 to formula 3), naphthalene-diyl (for example, the following formula 4 to formula 13), anthracene-diyl (for example, the following formulas 14 to 19), biphenyl-diyl (for example, the following formulas 20 to 25), terphenyl-diyl (for example, the following formulas 26 to 25) Formula 28), condensed ring compound group (for example, the following formula 29 to formula 35), fluorene-diyl (for example, the following formula 36 to formula 38), and benzofluorene-diyl (for example, the following formula 39 ~Formula 46).

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

In Formula 1 to Formula 46, R has the same meaning as above.

In the compound of this embodiment, the second structural unit CU2 is preferably selected from the group consisting of a divalent group containing an unsaturated bond and a group represented by the following formulas (VI-1) to formula (VI-12) Among the structural units in the group, the structural unit is more preferably selected from the group consisting of groups represented by formula (VI-10) to formula (VI-12).

[Chemical 35]

In Formula (VI-1) to Formula (VI-12), X ¹ , X ² , Z ¹ , Z ² and R are as defined above. When there are two R's, the two R's may be the same or different from each other.

As a more specific preferred example of the second structural unit CU2, a structural unit represented by the following formula can be cited. These structural units may further have substituents.

[Chemical 36]

In the compound of this embodiment, B ¹ contains one or more structural units, at least one of the one or more structural units is the first structural unit CU1, and the remaining structural units other than the first structural unit CU1 are the second structural units. Constituent unit CU2.

The combination and arrangement of the first structural unit CU1 and the second structural unit CU2 included in B ¹ are not particularly limited, provided that a π conjugate system can be formed.

B ¹ is preferably a divalent group having any one structure selected from the group consisting of structures represented by the following formula (VII-1) to formula (VII-16). -CU1- (VII-1) -CU1-CU1- (VII-2) -CU1-CU2- (VII-3) -CU1-CU1-CU1- (VII-4) -CU1-CU2-CU1- (VII- 5) -CU1-CU1-CU2- (VII-6) -CU1-CU2-CU2- (VII-7) -CU2-CU1-CU2- (VII-8) -CU1-CU1-CU1-CU1- (VII- 9) -CU1-CU1-CU1-CU2- (VII-10) -CU1-CU1-CU2-CU1- (VII-11) -CU1-CU1-CU2-CU2- (VII-12) -CU1-CU2-CU1 -CU2- (VII-13) -CU1-CU2-CU2-CU1- (VII-14) -CU1-CU2-CU2-CU2- (VII-15) -CU2-CU1-CU2-CU2- (VII-16)

In formula (VII-1) to formula (VII-16), CU1 represents the first structural unit CU1, CU2 represents the second constituent unit CU2. When there are two or more CU1s, the two or more CU1s may be the same or different from each other. When there are two or more CU2s, the two or more CU2s may be the same or different from each other.

Among the formulas (VII-1) to formula (VII-16), it is preferable that the formula is represented by formula (VII-1) to formula (VII-8), formula (VII-15) and formula (VII-16) The divalent group of the structure is preferably a formula (VII-1), formula (VII-3), formula (VII-7), formula (VII-8), formula (VII-15) and formula (VII- 16) The divalent base of the structure represented.

The total number of the first structural unit CU1 and the second structural unit CU2 that can be included in B ¹ is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 7 or less, preferably 5 or less , preferably 4 or less. The number of first structural units CU1 that can be included in B ¹ is usually 5 or less, preferably 3 or less, and more preferably 1. The number of second structural units CU2 that can be included in B ¹ is usually 5 or less, preferably 3 or less, and more preferably 1 or less.

Specific preferred examples of B ¹ include divalent groups represented by the following formula.

[Chemical 37]

[Chemical 38]

[Chemical 39]

[Chemical 40]

[Chemical 41]

[Chemical 42]

In the formula, R is as defined above.

(3) Specific examples of non-fullerene compounds Specific examples of the non-fullerene compound represented by formula (I) in this embodiment include compounds represented by the following formula.

[Chemical 43]

[Chemical 44]

[Chemical 45]

[Chemical 46]

[Chemical 47]

[Chemical 48]

More specific preferred examples of the non-fullerene compound represented by Formula (I) in this embodiment include compounds represented by the following formulas N-1 to Formula N-7.

[Chemical 49]

[Chemical 50]

2. Method for producing non-fullerene compounds. The non-fullerene compounds of this embodiment are also shown in the synthesis examples described below. For example, two or more raw material compounds that can constitute A ¹ and B ¹ described above can be used. And manufactured (synthesized) by any suitable method previously known.

In this embodiment, the active layer of the photoelectric conversion element may contain only the non-fullerene compound of this embodiment, particularly as an n-type semiconductor material, or may further contain compounds other than the non-fullerene compound of this embodiment. As an n-type semiconductor material. Compounds other than the non-fullerene compound of this embodiment that may be further included as the n-type semiconductor material may be low molecular compounds or high molecular compounds.

Examples of n-type semiconductor materials (electron-accepting compounds) other than the "non-fullerene compound of the present embodiment" which are low molecular compounds include oxadiazole derivatives, anthraquinonedimethane and its derivatives, and benzene. Quinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, Benzoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and phenanthrene derivatives such as 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline.

Examples of n-type semiconductor materials other than the "non-fullerene compound of this embodiment" which are polymer compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, side chains or Polysiloxane derivatives with aromatic amine structure in the main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polyethylene Thiophenyl vinylethylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

Compounds that are n-type semiconductor materials other than the "non-fullerene compound of this embodiment" may include fullerene derivatives.

Here, the fullerene derivative refers to at least a part of the fullerenes (C ₆₀ fullerene, C ₇₀ fullerene, C ₇₆ fullerene, C ₇₈ fullerene and C ₈₄ fullerene). Modified compounds. In other words, it refers to a compound having one or more groups attached to a fullerene skeleton. Hereinafter, the fullerene derivative of C ₆₀ fullerene may be specifically called "C ₆₀ fullerene derivative", and the fullerene derivative of C ₇₀ fullerene may be called "C ₇₀ fullerene derivative". "thing".

Fullerene derivatives other than the "non-fullerene compound of the present embodiment" that can be used as n-type semiconductor materials are not particularly limited as long as they do not impair the object of the present invention.

Specific examples of C ₆₀ fullerene derivatives that can be used as n-type semiconductor materials other than the "non-fullerene compound of the present embodiment" include the following compounds.

[Chemistry 51]

In the formula, R is as defined above. When there are multiple R's, the multiple R's may be the same or different.

Examples of C ₇₀ fullerene derivatives include the following compounds.

[Chemistry 52]

3. Photoelectric conversion element The photoelectric conversion element of this embodiment is a photoelectric conversion element including an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material, and as the n-type semiconductor material The compounds of this embodiment described above are also included.

According to the photoelectric conversion element of this embodiment, by having the above structure, characteristics such as external quantum efficiency and photoelectric conversion efficiency of the photoelectric conversion element can be effectively improved.

Here, a structural example that can be adopted by the photoelectric conversion element of this embodiment will be described. FIG. 1 is a diagram schematically showing the structure of a photoelectric conversion element according to this embodiment.

As shown in FIG. 1 , the photoelectric conversion element 10 is provided on the supporting substrate 11 . The photoelectric conversion element 10 includes an anode 12 provided in contact with the support substrate 11 , a hole transport layer 13 provided in contact with the anode 12 , and an active layer 13 in contact with the hole transport layer 13 . layer 14 , an electron transport layer 15 provided in contact with the active layer 14 , and a cathode 16 provided in contact with the electron transport layer 15 . In the above-described structural example, a sealing member 17 is further provided in contact with the cathode 16 . Hereinafter, the structural elements that can be included in the photoelectric conversion element of this embodiment will be described in detail.

(Substrate) Photoelectric conversion elements are usually formed on a substrate (support substrate). In addition, it may be further sealed by a substrate (sealing substrate). One of a pair of electrodes including an anode and a cathode is usually formed on the substrate. The material of the substrate is not particularly limited as long as it does not undergo chemical change when forming a layer containing an organic compound.

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

(electrode) The photoelectric conversion element includes an anode and a cathode as a pair of electrodes. In order to allow light to enter, at least one of the anode and the cathode is preferably a transparent or translucent electrode.

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

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 lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, and europium. , ytterbium, ytterbium and other metals, and alloys of two or more of these; or one or more of these metals are selected from gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin. Alloys of more than one metal in the group; graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

(active layer) It is assumed that the active layer included in the photoelectric conversion element of this embodiment has a bulk heterojunction type structure and contains a p-type semiconductor material and an n-type semiconductor material, and the active layer contains the non-fullerene of this embodiment. The compound serves as an n-type semiconductor material (details will be described later).

In this embodiment, the thickness of the active layer is not particularly limited. Taking into account the balance between suppression of dark current and extraction of generated photocurrent, the thickness of the active layer can be set to any appropriate thickness. In particular, from the viewpoint of further reducing dark current, the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and further preferably 200 nm or more. In addition, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, further preferably 1 μm or less.

Here, as a material for the active layer of this embodiment, a p-type semiconductor material that can be suitably used in combination with the n-type semiconductor material that is the non-fullerene compound of this embodiment has been described.

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

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

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

In this embodiment, the p-type semiconductor material is preferably a π-conjugated polymer compound (also called D-A type conjugated polymer compounds). Furthermore, which one is the donor constituent unit or the acceptor constituent unit can be relatively determined based on the energy level of HOMO or LUMO.

Here, the donor constituent unit is a constituent unit with an excess of π electrons, and the acceptor constituent unit is a constituent unit with a deficiency of π electrons.

In this embodiment, the structural units that can constitute the p-type semiconductor material also include structural units in which the donor structural unit and the acceptor structural unit are directly bonded, and the donor structural unit and the acceptor structural unit are bonded through any suitable A structural unit formed by bonding spacers (bases or structural units).

Examples of p-type semiconductor materials that are polymer compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, and 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, polyfluorene and its derivatives things.

The p-type semiconductor material of this embodiment is preferably a polymer compound containing a structural unit represented by the following formula (VIII). In this embodiment, the structural unit represented by the following formula (VIII) is generally a donor structural unit.

[Chemistry 53]

In formula (VIII), Ar ⁵ and Ar ⁶ represent an optionally substituted trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulas (Z-1) to (Z-7).

[Chemistry 54]

In formula (Z-1) to formula (Z-7), R is as defined above. In each of Formula (Z-1) to Formula (Z-7), when two R are present, the two R may be the same as or different from each other.

Among the aromatic heterocycles that can constitute Ar ⁵ and Ar ⁶ , in addition to the monocyclic and condensed rings in which the heterocycle itself shows aromaticity, it also includes the heterocyclic ring constituting the ring that does not show aromaticity itself but is in the heterocyclic ring. Rings with condensed aromatic rings.

The aromatic heterocycles that can constitute Ar ⁵ and Ar ⁶ may each be a single ring or a condensed ring. When the aromatic heterocyclic ring is a fused ring, all of the rings constituting the fused ring may be fused rings having aromatic properties, or only a part thereof may be fused rings having aromatic properties. In the case where the rings have multiple substituents, the substituents may be the same or different.

Specific examples of the aromatic carbocyclic ring that can constitute Ar ⁵ and Ar ⁶ include benzene ring, naphthalene ring, anthracene ring, condensed tetraphenyl ring, condensed pentaphenyl ring, pyrene ring and phenanthrene ring, preferably benzene ring and A naphthalene ring is more preferably a benzene ring and a naphthalene ring, and further preferably a benzene ring. These rings may have substituents.

Specific examples of the aromatic heterocyclic ring include the ring structures of the compounds described as aromatic heterocyclic compounds, including: oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, and thiophene ring. , pyrrole ring, phospholane ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring and dibenzophosphorus Heterocyclopentadiene ring, as well as phenoxazine ring, phenthiazine ring, dibenzoborole ring, dibenzosilole ring and benzopyran ring. These rings may have substituents.

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

[Chemical 55]

In formula (VIII-1), formula (VIII-2) and formula (VIII-3), Ar ⁵ , Ar ⁶ and R are as defined above.

Specific examples of suitable structural units represented by formula (VIII) include structural units represented by the following formulas.

[Chemical 56]

In the above formula, R is as defined above. When there are two R's, the two R's may be the same or different.

More specific examples of preferred structural units represented by formula (VIII) include structural units represented by the following formulas.

[Chemistry 57]

In this embodiment, the polymer compound as the p-type semiconductor material preferably contains a structural unit represented by the following formula (IX). In this embodiment, the structural unit represented by the following formula (IX) is usually a receptor structural unit.

[Chemical 58]

In formula (IX), Ar ⁷ represents a divalent aromatic heterocyclic group.

The number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar ⁷ is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20.

The divalent aromatic heterocyclic group represented by Ar ⁷ may have a substituent. Examples of the substituents that the divalent aromatic heterocyclic group represented by Ar ⁷ may have include: a halogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, and an alkyl group that may have a substituent. Oxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted monovalent heterocyclic group, optionally substituted substituted amino group , a acyl group that may have a substituent, an imine residue that may have a substituent, a amide group that may have a substituent, a amide group that may have a substituent, a substituted oxycarbonyl group that may have a substituent, Alkenyl group which may have a substituent, alkynyl group which may have a substituent, a cyano group and a nitro group.

As the structural unit represented by formula (IX), structural units represented by the following formula (IX-1) to formula (IX-10) are preferred.

[Chemistry 59]

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

From the viewpoint of the availability of the raw material compound, it is preferable that X ¹ and X ² in Formula (IX-1) to Formula (IX-10) are both sulfur atoms.

Furthermore, as mentioned above, the structural units represented by Formula (IX-1) to Formula (IX-10) usually function as receptor structural units. However, it is not limited to this. In particular, the structural units represented by formula (IX-4), formula (IX-5) and formula (IX-7) can also function as donor structural units.

In this embodiment, the p-type semiconductor material is preferably a π-conjugated polymer compound including a structural unit containing a thiophene skeleton and a π-conjugated system.

Specific examples of the divalent aromatic heterocyclic group represented by Ar ⁷ include groups represented by the above-mentioned formula (101) to formula (191). These groups may further have substituents.

The polymer compound as the p-type semiconductor material of the present embodiment is preferably π containing a structural unit represented by formula (VIII) as a donor structural unit and a structural unit represented by formula (IX) as an acceptor structural unit. Conjugated polymer compounds.

In the polymer compound as the p-type semiconductor material of this embodiment, the polymer compound as the p-type semiconductor material may include the structural unit represented by the already described formula (VIII) and the structure represented by the following formula (IX) A structure composed of connected units serves as a structural unit.

The polymer compound as the p-type semiconductor material of this embodiment may contain two or more structural units represented by formula (VIII), or may contain two or more structural units represented by formula (IX).

For example, from the viewpoint of improving solubility in a solvent, the polymer compound as the p-type semiconductor material of this embodiment may contain a structural unit represented by the following formula (X).

[Chemical 60]

In formula (X), Ar ⁸ represents an aryl group.

The aryl group represented by Ar ⁸ refers to an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. Aromatic hydrocarbons also include compounds having condensed rings, and compounds in which two or more selected from the group consisting of independent benzene rings and condensed rings are bonded directly or via a divalent group such as a vinyl vinyl group.

Examples of the substituents that the aromatic hydrocarbon may have include the same substituents as those exemplified as the substituents that the heterocyclic compound may have.

The number of carbon atoms of the aryl group represented by Ar ⁸ does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 20. The aryl group containing a substituent usually has 6 to 100 carbon atoms.

Examples of the aryl group represented by Ar ⁸ include phenylene group (for example, the following formulas 1 to 3), naphthalene-diyl (for example, the following formulas 4 to 13), anthracene-diyl (For example, the following formulas 14 to 19), biphenyl-diyl (for example, the following formulas 20 to 25), terphenyl-diyl (for example, the following formulas 26 to 28), condensed ring compounds group (for example, the following formulas 29 to 35), fluorene-diyl (for example, the following formulas 36 to 38), and benzofluorene-diyl (for example, the following formulas 39 to 46).

[Chemical 61]

[Chemical 62]

[Chemical 63]

[Chemical 64]

[Chemical 65]

[Chemical 66]

[Chemical 67]

[Chemical 68]

In the formula, R is as defined above. Multiple R's may be the same or different.

The structural unit represented by formula (X) is preferably a structural unit represented by the following formula (X-1) and formula (X-2).

[Chemical 69]

In formula (X-1), R is defined as described above. There are two R's that may be the same or different.

The structural unit constituting the polymer compound that is the p-type semiconductor material may be a structural unit in which two or more structural units selected from the above-mentioned structural units are connected in combination.

When the polymer compound as a p-type semiconductor material contains the structural unit represented by formula (VIII) and/or the structural unit represented by formula (IX), when the amount of all the structural units contained in the polymer compound is assumed to be When it is 100 mol%, the total amount of the structural unit represented by formula (VIII) and the structural unit represented by formula (IX) is usually 20 mol% to 100 mol%, which increases the electric charge of the p-type semiconductor material. From the viewpoint of transmittance, 40 mol% to 100 mol% is preferred, and 50 mol% to 100 mol% is more preferred.

Specific examples of the polymer compound of the p-type semiconductor material of this embodiment include polymer compounds represented by the following formulas (P-1) to (P-18).

[Chemical 70]

[Chemical 71]

[Chemical 72]

[Chemical 73]

[Chemical 74]

[Chemical 75]

[Chemical 76]

In the above formula, R is as defined above. Multiple R's may be the same or different.

If the exemplified polymer compound is used as a p-type semiconductor material, it is possible to suppress a decrease in EQE with respect to a heat treatment in a manufacturing step of a photoelectric conversion element or a step of assembling a photoelectric conversion element into a device to which the photoelectric conversion element is applied, or the like. Further increasing EQE can improve the heat resistance of photoelectric conversion elements.

(middle layer) As shown in FIG. 1 , the photoelectric conversion element of this embodiment preferably includes a charge transport layer (electron transport layer, hole transport layer, electron injection layer) as a component for improving characteristics such as photoelectric conversion efficiency. , hole injection layer) and other intermediate layers (buffer layer).

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

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

Sometimes the hole transport layer provided in contact with the anode is specifically called a hole injection layer. The hole transport layer (hole injection layer) provided in connection with the anode has the function of promoting the injection of holes into the anode. The hole transport layer (hole injection layer) can be connected to the active layer.

The hole transport layer contains a hole transport material. Examples of hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, and tungsten oxide (WO ₃ ) and molybdenum oxide (MoO ₃ ).

The intermediate layer may be formed by any suitable formation method previously known. The intermediate layer can be formed by a vacuum evaporation method or a coating method similar to the formation method of the active layer.

The photoelectric conversion element of this embodiment preferably has a structure in which the middle layer is an electron transport layer and has a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode laminated in order to be connected to each other. .

As shown in FIG. 1 , the photoelectric conversion element of this embodiment preferably includes an electron transport layer as an intermediate layer between the cathode and the active layer. The electron transport layer has the function of transporting electrons from the active layer to the cathode. The electron transport layer can be connected to the cathode. The electron transport layer can also be connected to the active layer.

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

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

Examples of polyalkyleneimine and its derivatives include ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, and pentyleneimine by conventional methods. A kind of alkylene imine having 2 to 8 carbon atoms, especially alkylene imine having 2 to 4 carbon atoms, such as alkylene imine, hexylene imine, heptyl imine, and octyl imine. Or polymers obtained by polymerizing two or more types, and polymers obtained by reacting these with various compounds and chemically modifying them. As polyalkyleneimine and its derivatives, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferred.

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

Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferred, and zinc oxide is particularly preferred.

Examples of other electron transporting materials include poly(4-vinylphenol) and perylenediamide.

(Sealing component) The photoelectric conversion element of this embodiment further includes a sealing member, and is preferably a sealed body sealed by the sealing member. Any suitable previously known member may be used as the sealing member. Examples of the sealing member include a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as UV curable resin.

The sealing member may also be a sealing layer having a layer structure of more than one layer. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.

The sealing layer is preferably formed of a material that has a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials for the sealing layer include trifluorinated polyethylene, polyethylene trifluoride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, and grease. Organic materials such as cyclic polyolefin and ethylene-vinyl alcohol copolymer, inorganic materials such as silicon oxide, silicon nitride, alumina, diamond-like carbon, etc.

The sealing member is made of a material that can withstand heat treatment that is usually performed when being assembled into a device to which a photoelectric conversion element is applied, such as in the application examples described below.

(Use of photoelectric conversion element) Examples of applications of the photoelectric conversion element of this embodiment include photodetection elements and solar cells. More specifically, the photoelectric conversion element of this embodiment can irradiate light from the transparent or translucent electrode side with a voltage (reverse bias voltage) applied between the electrodes, thereby allowing photocurrent to flow, and can be used as light The detection element (light sensor) operates. In addition, it can also be used as an image sensor by gathering multiple light detection elements. In this way, the photoelectric conversion element of this embodiment can be particularly suitably used as a photodetection element.

In addition, the photoelectric conversion element of this embodiment can generate photoelectromotive force between electrodes by irradiating light, and can operate as a solar cell. A solar cell module can also be made by gathering multiple photoelectric conversion elements.

(Application examples of photoelectric conversion elements) The photoelectric conversion element of this embodiment can be suitably used as a light detection element in detection parts included in various electronic devices such as workstations, personal computers, portable information terminals, room entry and exit management systems, digital cameras, and medical equipment.

The photoelectric conversion element of this embodiment can be suitably applied to solid-state imaging devices such as X-ray imaging devices and complementary metal oxide semiconductor (CMOS) image sensors included in the exemplary electronic devices. A biological information authentication device that detects some predetermined characteristics of a living body such as an image detection unit (such as an image sensor such as an X-ray sensor), a fingerprint detection unit, a face detection unit, a vein detection unit, and an iris detection unit. In the detection part (such as a near-infrared sensor), the detection part of an optical biosensor such as a pulse oximeter, etc.

The photoelectric conversion element of this embodiment can be suitably applied to a time-of-flight (TOF) distance measuring device (TOF distance measuring device) as an image detection unit for a solid-state imaging device.

4. Manufacturing method of photoelectric conversion element The method of manufacturing the photoelectric conversion element of this embodiment is not particularly limited. The photoelectric conversion element of this embodiment can be manufactured by combining a forming method suitable for the materials selected when forming the constituent elements.

The method of manufacturing a photoelectric conversion element according to this embodiment may include a step of heating at a heating temperature of 100° C. or higher. More specifically, the active layer is formed by a step of heating at a heating temperature of 100° C. or higher, and/or after the step of forming the active layer, the step may include heating at a heating temperature of 100° C. or higher. processing steps.

Hereinafter, as an embodiment of the present invention, a method for manufacturing a photoelectric conversion element having a structure in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are sequentially connected to each other will be described.

(Steps to prepare substrate) In this step, for example, a supporting substrate provided with an anode is prepared. In addition, a substrate provided with a conductive thin film made of the material of the electrode described above is obtained from the market, and if necessary, the conductive film is patterned to form an anode, thereby preparing a support substrate provided with the anode.

In the method of manufacturing the photoelectric conversion element of this embodiment, the method of forming the anode when forming the anode on the supporting substrate is not particularly limited. The anode can be formed by any suitable method known in the past such as vacuum evaporation, sputtering, ion plating, plating, coating, etc. layer, hole transport layer).

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

The formation method of the hole transport layer is not particularly limited. From the viewpoint of further simplifying the steps of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable coating method known in the past. The hole transport layer can be formed, for example, by a coating method or a vacuum evaporation method using a coating liquid containing the material and solvent of the hole transport layer described above.

(Steps for forming active layer) In the method of manufacturing a photoelectric conversion element of this embodiment, an active layer is formed on the hole transport layer. The active layer as the main constituent element can be formed by any suitable previously known formation steps. In this embodiment, the active layer is preferably produced by a coating method using an ink composition (ink, coating liquid).

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

Step (i) As a method of applying the ink composition to the application object, any appropriate coating method can be used. As the coating method, slit coating, blade coating, spin coating, microgravure coating, gravure coating, rod coating, inkjet printing, nozzle coating or capillary coating are preferred. The coating method is more preferably a slit coating method, a spin coating method, a capillary coating method or a rod coating method, and further preferably a slit coating method or a spin coating method.

The ink composition used in the method of manufacturing a photoelectric conversion element of this embodiment contains at least one p-type semiconductor material and at least one n-type semiconductor material.

Therefore, the ink composition of this embodiment is preferably an ink composition for forming an active layer of a photoelectric conversion element. Hereinafter, the ink composition for forming an active layer according to this embodiment will be described. Furthermore, the ink composition for forming the active layer of this embodiment is preferably an ink composition for forming a bulk heterojunction active layer. Therefore, the ink composition for active layer formation includes a composition containing the non-fullerene compound of the present embodiment as the p-type semiconductor material or n-type semiconductor material described above. The ink composition for forming an active layer of this embodiment includes the composition and two or more solvents, and the two or more solvents include a first solvent and a solvent having a boiling point higher than that of the first solvent. the second solvent.

The ink composition for forming an active layer according to this embodiment includes a p-type semiconductor material, an n-type semiconductor material, and two or more solvents, the two or more solvents including a first solvent and a solvent having the above-mentioned A second solvent with a higher boiling point than the first solvent can form a better phase separation structure, and as a result, characteristics such as external quantum efficiency (EQE) can be further improved (details will be described later).

The ink composition for forming an active layer according to this embodiment uses a mixed solvent composed of a first solvent and a second solvent. Specifically, the ink composition of this embodiment contains a main solvent (first solvent) and an additional solvent (second solvent) as main components.

Here, the first solvent and the second solvent that can be suitably used in the ink composition for forming the active layer according to the present embodiment and their combinations, as well as the preparation of the ink composition, will be described.

(1) First solvent As the first solvent, it is preferable to use a solvent that can dissolve both the p-type semiconductor material and the n-type semiconductor material of the present embodiment and can dissolve any one of the semiconductor materials that is a non-fullerene compound represented by formula (I). solvent. The first solvent in this embodiment is preferably an aromatic hydrocarbon.

Examples of the first solvent include toluene, xylene (such as o-xylene, m-xylene, p-xylene), o-dichlorobenzene, and trimethylbenzene (such as mesitylene, 1,2,4-trimethylbenzene). Methylbenzene (pseudocumene)), butylbenzene (such as n-butylbenzene, 2nd butylbenzene, 3rd butylbenzene), methylnaphthalene (such as 1-methylnaphthalene), tetrahydronaphthalene and dimethylnaphthalene Hydroindene.

The first solvent may contain only one solvent, or may contain two or more solvents. Since the ink composition can be prepared more easily, it is preferable to use only one solvent as the first solvent.

The first solvent is preferably selected from toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-dichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, 2-butylbenzene, One or more of the group consisting of methylnaphthalene, tert-butylbenzene, methylnaphthalene, tetralin and indene, more preferably toluene, o-xylene, m-xylene, p-xylene, o-dichloro Benzene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, 2nd-butylbenzene, 3rd-butylbenzene, methylnaphthalene, tetralin or indene.

(2) Second solvent In this embodiment, the second solvent is a solvent having a higher boiling point than the boiling point of the first solvent already described. In addition, the second solvent is a solvent in which the polar term P (B ¹ ) of the Hansen solubility parameter of the compound containing B ¹ and the polar term P (S2) of the Hansen solubility parameter of the second solvent satisfy the following formula (III) In the solvent under the conditions shown, the terminal B ¹ formed by cutting the bond between B ¹ and A ¹ in the non-fullerene compound represented by the formula (I) has been terminated with a hydrogen atom. |P(B ¹ )-P(S2)|＞3.2(MPa ^0.5 ) (III)

In other words, the second solvent is a solvent with a higher boiling point than the boiling point of the first solvent such that the absolute value of the difference between the polar term P (B ¹ ) and the polar term P (S2) is greater than 3.2 (MPa ^0.5 ). Choice of solvent.

Here, Hansen solubility parameters (HSP) used as indicators related to the second solvent will be described.

(i) Hansen solubility parameter The so-called Hansen solubility parameter (HSP) is a type of solubility parameter and is used to explore solvents in organic compounds, study the solubility when mixing multiple organic compounds, and design additive formulations. Furthermore, the organic compounds also include polydispersed polymer compounds.

The Hansen solubility parameter includes three components: the dispersion term D, which can be an indicator of dispersion force due to Van der Waals interaction, the polar term P, which can be an indicator of inter-dipole force due to electrostatic interaction. These three components are hydrogen bond terms H which can be used as indicators of hydrogen bonding force. These components can be represented in three dimensions.

Regarding the definition and calculation method of Hansen solubility parameters, for example, by Charles M. Hansen, Hansen Solubility Parameters: Users Handbook (A Users Handbook) and B. John, Solubility Parameters ( B, John, Solubility parameters): theory and application, The Book and paper group annual Vol.3 (theory and application, The Book and paper group annual Vol.3) and it is known that the calculation can also be suitably applied in this embodiment method.

In addition, Hansen solubility parameters (dispersion term D, polarity term P and hydrogen bond term H) can be determined using commercially available computer software such as Hansen Solubility Parameters in Practice (HSPiP), based on the chemistry of the compound. Structure to figure out. Details of the calculation method will be described later.

As described above, the ink composition of this embodiment is an ink composition including at least one p-type semiconductor material, at least one n-type semiconductor material, and two or more solvents.

In the method of manufacturing a photoelectric conversion element, especially in the case of forming an active layer with a bulk heterojunction type structure, from the viewpoint of forming a good phase separation structure in the active layer, it is important to prepare the ink for forming the active layer. When making a composition, it is necessary to select a solvent for suitably mixing the p-type semiconductor material and the n-type semiconductor material.

Here, the solvent that should be selected is usually a good solvent with high solubility relative to the p-type semiconductor material and the n-type semiconductor material. However, in this embodiment, in addition to the first solvent that is a good solvent, a semiconductor material represented by the formula (I) that has been described above is used in addition to the first solvent. The solubility is smaller and the semiconductor material has a higher Boiling point of the second solvent.

After the ink composition of this embodiment is applied when forming the active layer, in order to complete the active layer, it is necessary to remove the solvent after application.

According to this embodiment, during the process of removing the solvent, a good solvent with greater solubility and lower boiling point, that is, the first solvent, evaporates first. At the time when the first solvent evaporates, the main remaining solvent is the first solvent. The second solvent has smaller solubility and higher boiling point for the non-fullerene compound represented by formula (I). It is believed that after the first solvent, which is a good solvent with a lower boiling point, is first removed, a second solvent with a smaller solubility and a higher boiling point of the non-fullerene compound represented by formula (I) remains, and then the second solvent also remains. be removed, which would greatly affect the formation of a good phase separation structure. That is, it is thought that a good phase separation structure can be formed by appropriately selecting a second solvent in which the solubility of the non-fullerene compound represented by formula (I) is smaller and the boiling point is higher than the first solvent.

According to this embodiment, by focusing on the polar term (P) of the Hansen solubility parameter, which is an index of the inter-dipole force, among the three components of the Hansen solubility parameter, the first solvent and the second solvent are selected, thereby forming a good The phase separation structure can improve the characteristics of photoelectric conversion elements, especially EQE.

(ii) Calculation method of Hansen solubility parameter Here, the computer software HSPiP is used to calculate the polar term (P) of the Hansen solubility parameter in this embodiment, and further, |P(B ¹ )-P(S2) of the formula (III) )|The calculation method is explained.

First, after determining the chemical structure of the compound to be calculated, the following procedures 1) to 3) are performed. Here, among the non-fullerene compounds of the formula (I) described above, a compound having a structure of “A ¹ -B ¹ ” will be described as an example.

1) First, imagine a "compound containing B ¹ ": in the determined chemical structure of the compound, cut off the bond between A ¹ and B ¹ and cut out the A ¹ part and the B ¹ part, thereby adding the end of the B ¹ part "Compounds containing B ¹ " are terminated by adding hydrogen atoms to the resulting bonds.

2) Then, use the computer software HSPiP to calculate the polar term P(B ² ) of the Hansen solubility parameter of the proposed compound containing B ¹ .

3) Next, calculate the absolute value of the value obtained by subtracting the polar term P(S2) of the Hansen solubility parameter of the second solvent from the calculated P(B ¹ ), which is |P(B ¹ )-P( S2)|.

Here, the value of P(S2) of the second solvent may be the value described in "Hansen solubility parameters in practice 4th edition".

For example, when the second solvent is acetophenone, the value of P(S2) is 9.0 (MPa ^0.5 ).

Furthermore, when two or more solvents are used as the second solvent, the value for the solvent with the highest boiling point may be used.

Here, the calculation of the polar term P (B ¹ ) will be described using compound N-1 as a specific example.

First, as in the procedure 1), a compound (B ¹ ) containing B ¹ represented by the following formula is assumed. B ¹ represented by the following formula is obtained by cutting A ¹ and B ¹ with respect to compound N-1. In the case of two bonds, hydrogen atoms are added to the bonding bonds generated on B ¹ to terminate them.

[Chemical 77]

Next, as in the above-mentioned procedure 2), the polar term P(B ¹ ) is calculated for compound B ¹ . In fact, when calculated as above, P(B ¹ ) is 1.7 (MPa ^0.5 ).

Therefore, in the case where the second solvent is, for example, acetophenone, the value of |P(B ¹ )-P(S2)| that can be calculated according to the above procedure 3) can be calculated to be 7.3.

In particular, the second solvent suitable for the ink composition for forming the bulk heterojunction active layer of the photoelectric conversion element is preferably a solvent in which the non-fullerene compound represented by the formula (I) described above is not easily soluble, that is, A poor solvent for the non-fullerene compound represented by formula (I). More specifically, the second solvent is preferably a poor solvent in which the solubility of the non-fullerene compound represented by formula (I) is less than 1 g/L. Alternatively, a second solvent may be used in which the difference between the polar term of the Hansen solubility parameter of the compound containing B ¹ and the polar term of the Hansen solubility parameter of the second solvent satisfies the relationship represented by the above formula (III).

The second solvent is not particularly limited, provided that it satisfies the above requirements. As the second solvent, the characteristics of the selected first solvent can be taken into consideration, and an appropriate selection can be made from previously known solvents. Not only one type of second solvent may be used, but two or more types of second solvent may be used.

If a solvent that satisfies the above requirements is used as the second solvent, a better phase separation structure can be formed, thereby improving the EQE and other characteristics of the manufactured photoelectric conversion element.

In this embodiment, from the viewpoint of forming a good phase separation structure and improving characteristics such as EQE, the value of |P(B ¹ )-P(S2)| is preferably greater than 3.2, and more preferably greater than 3.3.

In this embodiment, from the viewpoint of forming a good phase separation structure and improving characteristics such as EQE, the second solvent is preferably a solvent having a boiling point 30° C. or more higher than the boiling point of the first solvent already explained.

The second solvent is preferably an ether solvent, an aromatic hydrocarbon solvent, a ketone solvent or an ester solvent.

Examples of the second solvent include 1,2-dimethoxybenzene, ether solvents such as diphenyl ether and dibenzyl ether, 1,2,3,5-tetramethylbenzene, cyclohexylbenzene, 1- Aromatic hydrocarbon solvents such as methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone and phenyl acetone, ethyl acetate, butyl acetate, phenyl acetate, ethyl cellulose acetate, benzene Ester solvents such as methyl formate, butyl benzoate and benzyl benzoate.

Table 4 below shows the second solvent applicable to the ink composition of this embodiment and the value of the polar term P (S2) (unit: MPa ^0.5 ) of the Hansen solubility parameter.

[Table 4] (Table 4) Second solvent P(S2) acetone 10.4 Methyl ethyl ketone 9.0 cyclohexanone 8.4 Acetophenone 9.0 Ethyl acetate 5.3 Butyl acetate 3.7 Phenyl acetate 2.8 Cellulose acetate ethyl ester 5.1 Butyl benzoate 5.6 Methyl benzoate 8.2 1,2-Dimethoxybenzene 4.4 diphenyl ether 3.4 dibenzyl ether 3.4 Prophenyl acetone 6.3 Benzyl benzoate 5.1 1,2,3,5-Tetramethylbenzene 0.5 Cyclohexylbenzene 0.0 1-methylnaphthalene 0.8

As the second solvent, from the viewpoint of forming a better phase separation structure and further improving characteristics such as EQE, it is preferable to use, for example, acetophenone, butyl benzoate, methyl benzoate, 1,2-dimethoxy Benzene.

(3) Combination of first solvent and second solvent Examples of suitable combinations of the first solvent and the second solvent are shown in the following Table 5 together with the boiling point (°C).

[Table 5] (Table 5) First solvent (S1) Second solvent (S2) Tetralin (207℃) Butyl benzoate (250℃) Tetralin (207℃) 1-Methylnaphthalene (244℃) Pseudocumene (169℃) 1,2-Dimethoxybenzene (207℃) Pseudocumene (169℃) Butyl benzoate (250℃) Ortho-xylene (144℃) Methyl benzoate (199℃) Ortho-xylene (144℃) Acetophenone (202℃)

As described above, in the ink composition of this embodiment, examples of suitable combinations of the first solvent and the second solvent include: tetralin (first solvent) and butyl benzoate (second solvent) The combination of o-xylene (the first solvent) and methyl benzoate (the second solvent), the combination of o-xylene (the first solvent) and acetophenone (the second solvent) and pseudocumene (the first solvent) A combination of solvent) and 1,2-dimethoxybenzene (second solvent).

(4) Volume ratio of the first solvent to the second solvent From the viewpoint of forming a better phase separation structure and improving characteristics such as EQE, the volume ratio of the first solvent as the main solvent to the second solvent as the additional solvent (first solvent: second solvent) is preferably The ratio is in the range of 85:15 to 99:1, more preferably in the range of 90:10 to 98:2, and still more preferably in the range of 93:7 to 97:3.

(5) Any other solvent The solvent may also include any other solvent other than the first solvent and the second solvent described above. When the total mass of all solvents contained in the ink composition is 100 mass %, the content rate of any other solvent is preferably 5 mass % or less, more preferably 3 mass % or less, and still more preferably 1 mass % or less. . As any other solvent, a solvent with a higher boiling point than the second solvent is preferred.

(6) Any ingredients In addition to the first solvent, the second solvent, the p-type semiconductor material and the n-type semiconductor material, the ink composition may also contain a surfactant, an ultraviolet absorber, an antioxidant within the limit that does not impair the purpose and effect of the present invention. Optional components include an oxidizing agent, a sensitizer for sensitizing the function of generating charges using absorbed light, and a light stabilizer for increasing stability against ultraviolet rays.

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

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

The total concentration of the "p-type semiconductor material" and the "n-type semiconductor material" in the ink composition is usually 0.01 mass% or more, more preferably 0.02 mass% or more, still more preferably 0.25 mass% or more. In addition, the total concentration of the "p-type semiconductor material" and the "n-type semiconductor material" in the ink composition is usually 20 mass% or less, preferably 10 mass% or less, and more preferably 7.50 mass% or less.

The concentration of the "p-type semiconductor material" in the ink composition is usually 0.01 mass% or more, more preferably 0.02 mass% or more, and still more preferably 0.10 mass% or more. In addition, the concentration of the "p-type semiconductor material" in the ink composition is usually 10 mass% or less, more preferably 5.00 mass% or less, and still more preferably 3.00 mass% or less.

The concentration of the "n-type semiconductor material" in the ink composition is usually 0.01 mass% or more, more preferably 0.02 mass% or more, and still more preferably 0.15 mass% or more. In addition, the concentration of the "n-type semiconductor material" in the ink is usually 10 mass% or less, more preferably 5 mass% or less, and still more preferably 4.50 mass% or less.

(8) Preparation of ink composition In this embodiment, the ink composition can be prepared by any suitable method known previously. For example, a mixed solvent can be prepared by mixing the first solvent or the first solvent and the second solvent, and adding (conjugated) polymer compound (p-type semiconductor material) and formula (I) to the obtained mixed solvent. compound (n-type semiconductor material); a method of adding a p-type semiconductor material to a first solvent, adding an n-type semiconductor material to a second solvent, and then mixing the first solvent and the second solvent containing each material Wait to prepare.

The first solvent, the second solvent, the p-type semiconductor material and the n-type semiconductor material can be heated to a temperature lower than the boiling point of the solvent and mixed.

The first solvent, the second solvent, the p-type semiconductor material and the n-type semiconductor material can be mixed, and the obtained mixture can be filtered using a filter, and the obtained filtrate can be used. As the filter, for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.

The ink composition for forming the active layer is applied to a coating target selected based on the photoelectric conversion element and its manufacturing method. In the manufacturing step of the photoelectric conversion element, the ink composition for forming the active layer can be coated on the functional layer of the photoelectric conversion element where the active layer can exist. Therefore, the objects to be coated with the ink composition for forming the active layer differ 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, anode, hole transport layer, active layer, electron transport layer, and cathode are laminated, and the layers described further to the left are formed first, the composition of the ink for forming the active layer The coating object of the object is the hole transport layer. In addition, 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 layer described further to the left is formed first, the active layer forming layer is The ink composition is applied to the electron transport layer.

Step (ii) Any suitable method can be used as a method of removing the solvent from the coating film of the ink composition, that is, a method of removing the solvent from the coating film and curing the coating film. Examples of methods for removing solvents include direct heating using a hot plate in an inert gas environment such as nitrogen, drying methods such as hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

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

The execution conditions of the pre-baking step and the post-baking step, that is, conditions such as heating temperature and heat treatment time, can be set to any appropriate conditions taking into consideration the composition of the ink used, the boiling point of the solvent, etc.

In the manufacturing method of the photoelectric conversion element of this embodiment, specifically, for example, a heating plate can be used to perform the pre-baking step and the post-baking step in a nitrogen atmosphere.

The total heat treatment time in the prebaking step and the postbaking step can be set to 1 hour, for example.

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

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

The thickness of the active layer can be set to any suitable desired thickness by appropriately adjusting the solid content concentration in the ink composition and the conditions of steps (i) and/or (ii).

In addition to the steps (i) and (ii), the step of forming the active layer may also include other steps without impairing the purpose and effect of the present invention.

The manufacturing method of the photoelectric conversion element of this embodiment may be a method of manufacturing a photoelectric conversion element including a plurality of active layers, or may be a method of repeating steps (i) and (ii) multiple times.

(Steps for forming electron transport layer) The method of manufacturing a photoelectric conversion element according to this embodiment includes the step of forming an electron transport layer (electron injection layer) provided on the active layer.

The method of forming the electron transport layer is not particularly limited. From the viewpoint of further simplifying the steps of forming the electron transport layer, it is preferable to form the electron transport layer by any suitable vacuum evaporation method known in the past.

(Cathode formation step) The formation method of the cathode is not particularly limited. The cathode can be formed of the material of the exemplified electrode on the electron transport layer by any suitable method known in the art, such as coating, vacuum evaporation, sputtering, ion plating, plating. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.

(Steps for forming the sealed body) When forming the sealing body, in this embodiment, any suitable sealing material (adhesive) and substrate (sealing substrate) known in the past are used. Specifically, a sealing material such as a UV curable resin is applied to the supporting substrate so as to surround the periphery of the produced photoelectric conversion element, and the sealing material is attached without gaps, and then irradiation with UV light is used. A sealed body of the photoelectric conversion element can be obtained by sealing the photoelectric conversion element in the gap between the supporting substrate and the sealing substrate using a method suitable for the selected sealing material.

5. Manufacturing method of image sensor and biometric authentication device As described above, the photoelectric conversion element of this embodiment, particularly the photodetection element, can be incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device) to function. [Example]

Hereinafter, in order to explain this invention further in detail, an Example is shown. The present invention is not limited to the examples described below.

In this example, the polymer compounds shown in Table 6 below were used as p-type semiconductor materials (electron-donating compounds), and the compounds shown in Tables 7 and 8 below were used as n-type semiconductor materials (electron-accepting compounds). ).

[Table 6] (Table 6) polymer compounds chemical structure P-1

[Table 7] (Table 7) compound chemical structure N-1 N-2 N-3 N-4

[Table 8] (Table 8) compound chemical structure N-5 N-6 N-7

The polymer compound P-1, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2011/052709.

Compounds N-1 to N-7, which are n-type semiconductor materials, are synthesized and used as in the synthesis examples described below.

<Synthesis Example 1> (Synthesis of Compound 2) Compound 2 represented by the following formula was synthesized using compound 1 represented by the following formula.

[Chemical 78]

In a 300 mL four-necked flask in which the internal environment was replaced with nitrogen, 4.00 g (7.77) of Compound 1 synthesized by the method described in the literature (Dyes and Pigments, 2015, 112, 145.) was placed. mmol), 78 mL of tetrahydrofuran, and cool to -30°C.

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

Then, the temperature of the obtained solution was raised to normal temperature, and the mixture was further stirred at normal temperature for 3 hours to react, and then 3% sodium sulfite aqueous solution was added to stop the reaction.

The obtained reaction liquid was extracted with hexane, and then washed with water and a saturated sodium chloride aqueous solution to obtain an organic layer.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 4.16 g (7.01 mmol, yield 94.9%) of compound 2 as a light yellow oil.

Regarding the obtained compound 2, a nuclear magnetic resonance (NMR) spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.16 (d, J _HH =8.4 Hz, 4H), 7.10 (d, J _HH =8.4 Hz, 4H), 6.98 (d, J _HH =4.8 Hz, 1H), 6.75 (d, J _HH =4.8 Hz, 1H), 6.42 (s, 1H), 2.58 (t, 4H), 1.63-1.57(m, 4H), 1.36-1.27 (br, 12H), 0.87 (t, 6H) .

<Synthesis Example 2> (Synthesis of Compound 3) Compound 3 represented by the following formula was synthesized using compound 2 represented by the following formula.

[Chemical 79]

In a 100 mL three-necked flask whose internal environment was replaced with nitrogen, 4.13 g (6.96 mmol) of compound 2 and 70 mL of dehydrated tetrahydrofuran were added. After cooling the obtained solution to -70°C, n-butyllithium solution (1.64 mol/L, hexane solution) 4.13 mL, stir for 1 hour.

Next, while maintaining the reaction liquid at -70°C, 1.01 g (9.74 mmol) of trimethoxyborane was added, and stirring was performed for 2 hours.

Then, a 10 mass% acetic acid aqueous solution (30 mL) was added to the obtained reaction liquid, and liquid separation was performed using ethyl acetate, and the organic layer was extracted. To the obtained organic layer, add toluene (20 mL) and 1.25 g (10.4 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol, and use Dean-Stark. The tube was dehydrated for 30 minutes. Furthermore, the solvent was removed using a rotary evaporator, and 4.47 g of a crude product of compound 3 was obtained as a green oil.

<Synthesis Example 3> (Synthesis of Compound 5) Compound 5 represented by the following formula was synthesized using compound 3 and compound 4 represented by the following formula.

[Chemical 80]

In a 300 mL four-necked flask in which the internal environment was replaced with nitrogen, 1.00 g (1.43 mmol) of compound 4 synthesized by the method described in Japanese Patent Application Laid-Open No. 2013-43818 and 2.20 g (2.20 g) of compound 3 were placed. 3.43 mmol), 14 mL of tetrahydrofuran, and degassed by bubbling argon gas for 30 minutes.

Then, in a four-necked flask, put 0.105 g (dibenzylideneacetone) dipalladium (0) (0.11 mmol, 8 mol%) and 0.070 g (0.23 mmol) tris-tert-butylphosphonium tetrafluoroborate. , 16 mol%), 5 mL of tetrahydrofuran, and stir for 5 minutes.

Next, 14 mL of 3.0 M potassium phosphate aqueous solution was added to a four-necked flask, and the reaction solution was heated in an oil bath with a set temperature of 50° C. for 3 hours while stirring.

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

The obtained solution was dried using anhydrous sodium sulfate and filtered, and the solvent was evaporated under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 1.74 g (1.11 mmol, yield 78%) of compound 5 as a red oil.

Regarding the obtained compound 5, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.38 (s, 1H), 7.23-7.18 (m, 8H), 7.14-7.10 (m, 8H), 7.03-7.00 (m, 2H), 6.92 (s, 1H) , 6.79-6.77 (m, 2H), 6.58 (s, 1H), 6.53 (s, 1H), 2.62-2.57 (m, 8H), 2.19-2.11 (m, 2H), 1.71-1.56 (m, 10H) , 1.37-1.25 (m, 28H), 1.25-1.08 (br, 36H), 0.89-0.83 (m, 18H).

<Synthesis Example 4> (Synthesis of Compound 6) Compound 6 represented by the following formula was synthesized using compound 5 represented by the following formula.

[Chemical 81] In a 100 mL three-necked flask whose internal environment was replaced with nitrogen, 1.74 g (1.11 mmol) of compound 5 and 12 mL of chloroform were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 5.

Next, 0.43 g (3.33 mmol) of (chloromethylene)dimethylammonium chloride was placed in a three-necked flask, and the mixture was heated in an oil bath with a set temperature of 65° C. for 2 hours while stirring.

Then, after cooling the reaction solution, 20 mL of water was added, and the organic layer was separated and washed twice with a saturated sodium chloride aqueous solution. The obtained solution was dried using anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 1.63 g (1.01 mmol, yield 90.6%) of compound 6 as a dark red oil.

Regarding the obtained compound 6, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 9.76 (s, 1H), 9.75 (s, 1H), 7.46 (s, 1H), 7.37 (s, 1H), 7.36 (s, 1H), 7.21-7.12 (m , 16H), 7.00 (s, 1H), 6.61 (s, 1H), 6.58 (s, 1H), 2.63-2.58 (m, 8H), 2.21-2.13(m, 2H), 1.73-1.57 (m, 10H ), 1.37-1.26 (m, 28H), 1.24-1.09 (br, 36H), 0.89-0.83 (m, 18H).

<Synthesis Example 5> (Synthesis of Compound N-1) Compound N-1 represented by the following formula was synthesized using compound 6 and compound 7 represented by the following formula.

[Chemical 82]

In a 100 mL four-necked flask whose internal environment has been replaced with nitrogen, 0.57 g (0.35 mmol) of compound 6, 0.28 g (1.05 mmol) of compound 7, 10 mL of chloroform, and 0.003 g (0.04 mmol) of pyridine are placed, and the mixture is placed at 65 Heat in an oil bath at ℃ for 2 hours with stirring.

The obtained solution was cooled to normal temperature, and water was added to stop the reaction. The obtained solution was extracted with chloroform, washed twice with water, and once with a saturated sodium chloride aqueous solution to obtain an organic layer.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 0.64 g (0.30 mmol, yield 86.3%) of compound N-1 as a dark blue-green solid.

The NMR spectrum of the obtained compound N-1 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 8.74 (s, 1H), 8.73 (s, 1H), 8.69 (s, 1H), 8.68 (s, 1H), 7.91 (s, 1H), 7.90 (s, 1H ), 7.49 (s, 2H), 7.46 (s, 1H), 7.21-7.14 (m, 16H), 7.03 (s, 1H), 6.67 (s, 1H), 6.64 (s, 1H), 2.64-2.59 ( m, 8H), 2.24-2.17(m, 2H), 1.99-1.86 (m, 8H), 1.76-1.59 (m, 10H), 1.38-1.26 (m, 28H), 1.24-1.12 (br, 36H), 0.89-0.83 (m, 18H).

<Synthesis Example 6> (Synthesis of Compound 9) Compound 9 represented by the following formula is synthesized from compound 8 represented by the following formula.

[Chemical 83]

Into a 100 mL three-necked flask whose internal environment was replaced with nitrogen, 2.85 g (5.36 mmol) of compound 18 synthesized by the method described in paragraph [0271] of International Publication No. 2011/052709 and 27 mL of dehydrated tetrahydrofuran were added. After cooling the obtained solution to -70°C, 3.3 mL of n-butyllithium solution (1.64 mol/L, hexane solution) was added and stirred for 2 hours.

Next, while maintaining the reaction liquid at -70°C, 0.83 g (8.04 mmol) of trimethoxyborane was added, and stirring was performed for 2 hours.

Then, a 10 w% acetic acid aqueous solution (30 mL) was added to the obtained reaction liquid, and liquid separation was performed using ethyl acetate, and the organic layer was extracted. To the obtained organic layer, add toluene (20 mL) and 1.29 g (10.72 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol, and perform dehydration using a Dean-Stark tube 30 minute. Furthermore, the solvent was removed using a rotary evaporator, and 3.53 g of a crude product of compound 19 was obtained as a green oil.

<Synthesis Example 7> (Synthesis of Compound 11) Compound 11 represented by the following formula was synthesized using compound 9 and compound 10 represented by the following formula.

[Chemical 84]

Into a 100 mL four-necked flask in which the internal environment was replaced with nitrogen, 3.53 g (5.36 mmol) of Compound 9, the unrefined crude product obtained in Synthesis Example 6, purchased from Luminescence Technology Corp. .) 1.2 g (2.23 mmol) of purchased compound 10 and 22 mL of tetrahydrofuran were degassed by bubbling argon gas for 30 minutes.

In the obtained reaction solution, 0.164 g (0.179 mmol, 8 mol%) tris(dibenzylideneacetone)dipalladium(0) and 0.109 g (0.357 mmol) tris-tert-butylphosphonium tetrafluoroborate were added. , 16 mol%), stir for 5 minutes.

Next, 22 mL of 3.0 M potassium phosphate aqueous solution was further added to the reaction liquid, and the obtained reaction liquid was heated in an oil bath with a set temperature of 75° C. for 1 hour while stirring.

Then, after cooling the reaction solution, 100 mL of water and 100 mL of hexane were added, and liquid separation and washing were performed three times with water, and once with a saturated sodium chloride aqueous solution.

The obtained solution was dried with anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified using a silica gel column to obtain 2.11 g (1.49 mmol, yield 67%) of compound 11 as a dark red oil.

The NMR spectrum of the obtained compound 21 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.94 (s, 1H), 7.03 (dd, J _HH =9.2 Hz, 5.2 Hz, 2H), 6.85 (s, 1H), 6.81 (s, 1H), 6.68 (dd , J _HH =5.2 Hz, 1.6 Hz, 2H), 4.37 (t, J _HH =6.8 Hz, 2H), 1.95-1.78 (m, 10H), 1.44-1.22 (m, 100H), 0.86 (t, 15H) .

<Synthesis Example 8> (Synthesis of Compound 12) Compound 12 represented by the following formula is synthesized from compound 11 represented by the following formula.

[Chemical 85]

To a 100 mL four-necked flask in which the internal environment was replaced with nitrogen, 1.5 g (1.06 mmol) of compound 21 and 11 mL of methylene chloride were added and dissolved.

Next, 0.41 g (3.19 mmol) of (chloromethylene)dimethylammonium chloride was added to the obtained reaction liquid, and the mixture was heated and stirred for 3 hours in an oil bath with a set temperature of 40°C.

Then, after cooling the obtained reaction liquid, 20 mL of water was added, and liquid separation and washing were performed twice with a saturated sodium chloride aqueous solution.

The obtained solution was dried with magnesium sulfate and then filtered. The solvent was evaporated under reduced pressure to obtain a crude product. The obtained crude product was purified using a silica gel column to obtain the compound as a purple solid. 22 1.44 g (0.98 mmol, yield 92%).

The NMR spectrum of the obtained compound 22 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 9.78 (s, 1H), 9.77 (s, 1H), 7.95 (s, 1H), 7.29 (s, 1H), 7.28 (s, 1H), 6.90 (s, 1H ), 6.86 (s, 1H), 4.39 (t, J _HH =7.2 Hz, 2H), 1.97-1.79 (m, 10H), 1.46-1.22 (m, 100H), 0.86 (t, 15H).

<Synthesis Example 9> (Synthesis of Compound N-2) Compound N-2 represented by the following formula was synthesized using compound 12 and compound 13 represented by the following formula.

[Chemical 86]

In a 100 mL four-necked flask whose internal environment was replaced with nitrogen, 1.4 g (0.98 mmol) of compound 12, 0.78 g (2.95 mmol) of compound 13, 20 mL of chloroform, and 0.04 g (0.49 mmol) of pyridine were placed at 65 Heat in an oil bath at ℃ for 2 hours with stirring.

Next, the obtained solution was cooled to normal temperature, and water was added to stop the reaction. After the obtained solution was extracted with chloroform, it was washed twice with water and once with a saturated sodium chloride aqueous solution.

Then, the obtained organic layer was dried with magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified using a silica gel column to obtain 1.5 g (0.77 mmol, yield 95%) 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 H NMR (CDCl ₃ )] δ 8.57-8.51 (m, 4H), 7.81 (s, 1H), 7.77 (s, 1H), 7.73 (s, 1H), 7.29 (br, 2H), 6.96 (s , 1H), 6.88 (s, 1H), 4.50 (t, J _HH =7.2 Hz, 2H), 2.08-1.93 (m, 10H), 1.59-1.20 (m, 100H), 0.83 (t, 15H).

<Synthesis Example 10> (Synthesis of Compound 15) Compound 15 represented by the following formula was synthesized using compound 14 represented by the following formula.

[Chemical 83]

Into a 300 mL three-necked flask in which the internal environment was replaced with nitrogen, 10.2 g (16.7 mmol) of compound 14 synthesized by the method described in paragraphs [0269] to [0274] of Japanese Patent Application Laid-Open No. 2012-36357 was added. ), 170 mL of dehydrated tetrahydrofuran, cool the obtained solution to -70°C, add 10.9 mL (17.5 mmol) of n-butyllithium solution (1.6 mol/L, hexane solution), and stir for 1 hour.

Next, while maintaining the reaction liquid at -70°C, 4.39 g (23.4 mmol) of trimethoxyborane was added, and stirring was performed for 2 hours.

Then, 41.5 g of a 2 mass% acetic acid aqueous solution was added to the obtained reaction liquid, and liquid separation was performed using ethyl acetate, and the organic layer was extracted. To the obtained organic layer, add toluene (20 mL) and 3.00 g (25.1 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol, and perform dehydration using a Dean-Stark tube 30 minute. Furthermore, the solvent was removed using a rotary evaporator, and 11.2 g of a crude product of compound 15 was obtained as a green oil.

<Synthesis Example 11> (Synthesis of Compound 17) Compound 17 represented by the following formula was synthesized using compound 15 and compound 16 represented by the following formula.

[Chemical 88]

In a 300 mL four-necked flask in which the internal environment was replaced with nitrogen, 2.45 g of compound 16 synthesized by the method described in paragraphs [0202] to [0205] of Japanese Patent Application Laid-Open No. 2014-31364 ( 3.50 mmol), 5.30 g (8.05 mmol) of compound 15, and 100 mL of tetrahydrofuran, and degassed by bubbling argon gas for 30 minutes.

Then, in a four-necked flask, put 0.160 g (dibenzylideneacetone) dipalladium (0) (0.175 mmol, 5 mol%) and 0.213 g (0.700 mmol) tris-tert-butylphosphonium tetrafluoroborate. , 20 mol%), 15 mL of tetrahydrofuran, and stir for 5 minutes.

Next, 12 mL of 3.0 M potassium phosphate aqueous solution was added to the four-necked flask, and the reaction solution was heated in an oil bath with a set temperature of 75° C. for 1 hour while stirring.

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

The obtained solution was dried using anhydrous sodium sulfate and filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was purified using a silica gel column to obtain 4.97 g (3.11 mmol, yield 88.8%) of compound 17 in the form of red oil.

The NMR spectrum of the obtained compound 17 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.43 (s, 1H), 7.01 (d, J _HH =5.2 Hz, 1H), 7.00 (d, J _HH =5.2 Hz, 1H), 6.96 (s, 1H), 6.82 (s, 1H), 6.79 (s, 1H), 6.67 (d, J _HH =4.8 Hz, 1H), 6.66 (d, J _HH =4.8 Hz, 1H), 2.18 (m, 2H), 1.87 (m , 8H), 1.71 (m, 2H), 1.23 (br, 120H), 0.86 (m, 18H).

<Synthesis Example 12> (Synthesis of Compound 18) Compound 18 represented by the following formula was synthesized using compound 17 represented by the following formula.

[Chemical 89]

In a 300 mL three-necked flask whose internal environment was replaced with nitrogen, 4.96 g (3.10 mmol) of compound 17 and 150 mL of methylene chloride were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 17.

Next, 1.19 g (9.30 mmol) of (chloromethylene)dimethylammonium chloride was placed in a three-necked flask, and the mixture was heated in an oil bath with a set temperature of 40° C. for 2 hours while stirring.

Then, after cooling the reaction solution, 20 mL of water was added, and the organic layer was separated and washed twice with a saturated sodium chloride aqueous solution. The obtained solution was dried using anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 4.81 g (2.90 mmol, yield 93.7%) of compound 18 as a dark red solid.

The NMR spectrum of the obtained compound 18 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 9.783 (s, 1H) , 9.775 (s, 1H) , 7.53 (s, 1H) , 7.28 (s, 1H) , 7.27 (s, 1H) , 7.06 (s, 1H ), 6.87 (s, 1H), 6.85 (s, 1H), 2.22 (m, 2H), 1.90 (m, 8H), 1.74 (m, 2H), 1.21 (br, 120H), 0.86 (m, 18H) .

<Synthesis Example 13> (Synthesis of Compound N-3) Compound N-3 represented by the following formula was synthesized using compound 18 represented by the following formula and compound 13.

[Chemical 90]

In a 100 mL four-necked flask in which the internal environment was replaced with nitrogen, 0.828 g (0.500 mmol) of compound 18, 0.395 g (1.50 mmol) of compound 19, 25 mL of chloroform, and 0.396 g of pyridine (5.00 mmol) were placed, and the mixture was placed at 65 Heat in an oil bath at ℃ for 2 hours with stirring.

The obtained solution was cooled to normal temperature, and water was added to stop the reaction. The obtained solution was extracted with chloroform, washed twice with water, and once with a saturated sodium chloride aqueous solution to obtain an organic layer.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 0.752 g (0.350 mmol, yield 70.1%) of compound N-3 as a dark blue-green solid.

The NMR spectrum of the obtained compound N-3 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 8.74 (s, 4H), 7.92 (s, 1H), 7.91 (s, 1H), 7.62 (s, 1H), 7.40 (s, 1H), 7.39 (s, 1H ), 7.15 (s, 1H), 6.93 (s, 1H), 6.91 (s, 1H), 2.26 (m, 2H), 1.93 (m, 8H), 1.79 (m, 2H), 1.20 (br, 120H) , 0.86 (m, 18H).

<Synthesis Example 14> (Synthesis of Compound 21) Compound 21 represented by the following formula was synthesized using compound 20 represented by the following formula.

[Chemical 91]

In a 300 mL four-necked flask in which the internal environment was replaced with nitrogen, 5.02 g (12.0 mmol) of compound 20 synthesized by the method described in paragraphs [0261] to [0271] of International Publication No. 2011/052709 was placed. , 100 mL of tetrahydrofuran, cool to -30°C.

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

Then, the temperature of the obtained solution was raised to normal temperature, and the mixture was further stirred at normal temperature for 3 hours to react, and then 3% sodium sulfite aqueous solution was added to stop the reaction.

The obtained reaction liquid was extracted with hexane, and then washed with water and a saturated sodium chloride aqueous solution to obtain an organic layer.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 4.66 g (9.36 mmol, yield 78.0%) of compound 21 as a light yellow oil.

The NMR spectrum of the obtained compound 21 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 6.98 (d, J _HH =4.8 Hz, 1H), 6.66 (s, 1H), 6.65 (d, J _HH =4.8 Hz, 1H), 1.87-1.74 (m, 4H ), 1.41-1.23 (br, 24H), 0.86 (t, 6H).

<Synthesis Example 15> (Synthesis of Compound 22) Compound 22 represented by the following formula was synthesized using compound 21 represented by the following formula.

[Chemical 92]

In a 100 mL three-necked flask whose internal environment was replaced with nitrogen, 4.59 g (9.23 mmol) of compound 21 and 90 mL of dehydrated tetrahydrofuran were added. After cooling the obtained solution to -70°C, n-butyllithium solution (1.64 mol/L, hexane solution) 5.8 mL, stir for 1 hour.

Next, while maintaining the reaction liquid at -70°C, 2.43 g (12.9 mmol) of trimethoxyborane was added, and stirring was performed for 2 hours.

Then, a 10 mass% acetic acid aqueous solution (30 mL) was added to the obtained reaction liquid, and liquid separation was performed using ethyl acetate, and the organic layer was extracted. To the obtained organic layer, add toluene (20 mL) and 1.66 g (13.82 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol, and perform dehydration using a Dean-Stark tube 30 minute. Furthermore, the solvent was removed using a rotary evaporator, and 5.00 g of a crude product of compound 22 was obtained as a green oil.

<Synthesis Example 16> (Synthesis of Compound 24) Compound 24 represented by the following formula was synthesized using compound 22 and compound 23 represented by the following formula.

[Chemical 93]

In a 200 mL four-necked flask whose internal environment was replaced with nitrogen, 1.65 g (2.80 mmol) of compound 23 synthesized by the method described in the literature (ACS Omega 2017, 2, 4347.) was placed. , 3.83 g (7.00 mmol) of compound 22, 93 mL of tetrahydrofuran, and degassed by bubbling argon gas for 30 minutes.

Then, in a four-necked flask, add 0.128 g (0.140 mmol, 5 mol%) tris(dibenzylideneacetone)dipalladium(0) and 0.170 g (0.560 mmol) tris-tert-butylphosphonium tetrafluoroborate. , 20 mol%), 5 mL of tetrahydrofuran, and stir for 5 minutes.

Next, 9.3 mL of 3.0 M potassium phosphate aqueous solution was added to the four-necked flask, and the reaction solution was heated in an oil bath with a set temperature of 50° C. for 3 hours while stirring.

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

The obtained solution was dried using anhydrous sodium sulfate and filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was purified using a silica gel column to obtain 3.21 g (2.54 mmol, yield 90.6%) of compound 24 in the form of red oil.

The NMR spectrum of the obtained compound 24 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.44 (s, 1H), 7.03 (d, J _HH =4.0 Hz, 1H), 7.02 (d, J _HH =4.0 Hz, 1H), 6.97 (s, 1H), 6.83 (s, 1H), 6.80 (s, 1H), 6.89 (d, J _HH =4.8 Hz, 1H), 6.68 (d, J _HH =4.8 Hz, 1H), 2.23-2.16 (m, 2H), 1.94 -1.81 (m, 8H), 1.77-1.69 (m, 2H), 1.44-1.11 (br, 72H), 0.86-0.80 (m, 18H).

<Synthesis Example 17> (Synthesis of Compound 25) Compound 25 represented by the following formula was synthesized using compound 24 represented by the following formula.

[Chemical 94]

In a 100 mL three-necked flask whose internal environment was replaced with nitrogen, 3.41 g (2.70 mmol) of compound 24 and 80 mL of chloroform were placed, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 66.

Next, 1.04 g (8.10 mmol) of (chloromethylene)dimethylammonium chloride was placed in a three-necked flask, and the mixture was heated in an oil bath with a set temperature of 65° C. for 2 hours while stirring.

Then, after cooling the reaction solution, 20 mL of water was added, and the organic layer was separated and washed twice with a saturated sodium chloride aqueous solution. The obtained solution was dried using anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 2.97 g (2.25 mmol, yield 83.3%) of compound 25 as a dark red solid.

The NMR spectrum of the obtained compound 25 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 9.79 (s, 1H), 9.78 (s, 1H), 7.53 (s, 1H), 7.29 (s, 1H), 7.28 (s, 1H), 7.06 (s, 1H ), 6.87 (s, 1H), 2.25-2.17(m, 2H), 1.96-1.84 (m, 8H), 1.78-1.71 (m, 2H), 1.44-1.12 (br, 72H), 0.87-0.79 (m , 18H).

<Synthesis Example 18> (Synthesis of Compound N-4) Compound N-4 represented by the following formula was synthesized using compound 13 represented by the following formula and compound 25.

[Chemical 95]

In a 100 mL four-necked flask in which the internal environment was replaced with nitrogen, 0.858 g (0.650 mmol) of compound 67, 0.513 g (1.95 mmol) of compound 12, 30 mL of chloroform, and 0.514 g (6.50 mmol) of pyridine were placed, and the mixture was placed at 65 Heat in an oil bath at ℃ for 2 hours with stirring.

The obtained solution was cooled to normal temperature, and water was added to stop the reaction. The obtained solution was extracted with chloroform, washed twice with water, and once with a saturated sodium chloride aqueous solution to obtain an organic layer.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 0.967 g (0.534 mmol, yield 82.2%) of compound N-4 as a dark blue-green solid.

Regarding the obtained compound N-4, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 8.74 (s, 4H), 7.92 (s, 1H), 7.91 (s, 1H), 7.63 (s, 1H), 7.40 (s, 1H), 7.38 (s, 1H ), 7.15 (s, 1H), 6.94 (s, 1H), 6.91 (s, 1H), 2.29-2.22(m, 2H), 1.99-1.86 (m, 8H), 1.82-1.75 (m, 2H), 1.44-1.14 (br, 72H), 0.92-0.80 (m, 18H).

<Synthesis Example 19> (Synthesis of Compound 27) Compound 27 represented by the following formula was synthesized using compound 26 represented by the following formula.

[Chemical 96]

In a 100 mL three-necked flask in which the internal environment was replaced with nitrogen, 0.746 g (0.450 mmol) of compound 26 and tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide were placed 0.349 g (0.945 mmol), 20 mL of tetrahydrofuran, cool to 0°C.

Then, add 0.072 g (1.80 mmol) of sodium hydride, raise the temperature to room temperature, and stir for one and a half hours.

Cool the reaction solution to 0°C again, add 10% hydrochloric acid, raise the temperature to room temperature, and stir for 2 hours. Further, 15 mL of hexane was added to the reaction solution, and the organic layer was separated and washed once with water and twice with saturated sodium chloride aqueous solution. The obtained solution was dried using anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 0.703 g (0.412 mmol, yield 91.4%) of compound 27 as a purple-red oil.

The NMR spectrum of the obtained compound 27 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 9.614 (d, J _HH =8.0 Hz, 1H), 9610 (d, J _HH =8.0 Hz, 1H), 7.50 (s, 1H), 7.433 (d, J _HH = 15.6 Hz, 1H), 7.426 (d, J _HH =15.6 Hz, 1H), 7.03 (s, 1H), 6.93 (s, 1H), 6.92 (s, 1H), 6.85 (s, 1H), 6.83 (s , 1H), 6.457 (dd, J _HH =8.0 Hz, 15.6 Hz, 1H), 6.453 (dd, J _HH =8.0 Hz, 15.6 Hz, 1H), 2.24-2.17 (m, 2H), 1.95-1.82 (m , 8H), 1.78-1.70 (m, 2H), 1.41-1.11 (br, 120H), 0.88-0.83 (m, 18H).

<Synthesis Example 20> (Synthesis of Compound N-5) Compound N-5 represented by the following formula was synthesized using compound 13 represented by the following formula and compound 27.

[Chemical 97]

In a 100 mL four-necked flask in which the internal environment has been replaced with nitrogen, 1.00 g (0.585 mmol) of compound 7, 0.462 g (0.585 mmol) of compound 13, 29 mL of chloroform, and 0.463 g of pyridine (5.85 mmol) were placed, and the mixture was placed at 65 Heat in an oil bath at ℃ for 2 hours with stirring.

The obtained solution was cooled to normal temperature, and water was added to stop the reaction. The obtained solution was extracted with chloroform, washed twice with water, and once with a saturated sodium chloride aqueous solution to obtain an organic layer.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 0.982 g (0.447 mmol, yield 76.4%) of compound N-5 as a dark blue-green solid.

Regarding the obtained compound N-5, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 8.74 (s, 2H), 8.55-8.40 (m, 4H), 7.92 (s, 2H), 7.55 (s, 1H), 7.41 (d, J _HH =14 Hz, 2H), 7.06 (d, J _HH =14 Hz, 2H), 7.05 (s, 2H), 6.87 (s, 2H), 6.85 (s, 2H), 2.28-2.20 (m, 2H), 1.93-1.89 ( m, 8H), 1.81-1.74 (m, 2H), 1.27-1.14 (br, 120H), 0.87-0.83 (m, 18H).

<Synthesis Example 21> (Synthesis of Compound 29) Compound 29 represented by the following formula was synthesized from compound 28 represented by the following formula.

[Chemical 98]

In a 1 L four-necked flask in which the internal environment was replaced with nitrogen, 13.30 g (24.50 mmol) of compound 28 synthesized by the method described in paragraph [0203] of Japanese Patent Application Laid-Open No. 2014-31364 and tetrahydrofuran were placed. 490 mL, cool to 0°C.

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

Then, the temperature of the obtained solution was raised to normal temperature, and the mixture was further stirred at normal temperature for 3 hours to react, and then 3% sodium sulfite aqueous solution was added to stop the reaction.

The obtained reaction liquid was extracted with hexane, and then washed with water and a saturated sodium chloride aqueous solution.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 10.1 g (16.2 mmol, yield 66.3%) of compound 29 as a light yellow oil.

Regarding the obtained compound 29, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.44 (d, J _HH =5.6 Hz, 1H), 7.07 (d, J _HH =5.6 Hz, 1H), 6.95 (s, 1H), 2.16 (m, 2H), 1.72 (m, 2H), 1.21 (br, 40H), 0.86 (t, 6H).

<Synthesis Example 22> (Synthesis of Compound 31) Compound 31 represented by the following formula was synthesized using compound 29 represented by the following formula and compound 30.

[Chemical 99]

In a 300 mL four-necked flask in which the internal environment was replaced with nitrogen, 5.23 g (6.65 mmol) of compound 30 synthesized by the method described in paragraphs [0139] to [0141] of International Publication No. 2011/052709 was placed. , Compound 29 9.51 g (15.3 mmol), tetralin 120 mL, and degassed by bubbling argon gas for 30 minutes.

Then, in a four-necked flask, put 0.304 g (dibenzylideneacetone) dipalladium (0) (0.333 mmol, 5 mol%) and 0.405 g (1.33 mmol) tris-tert-butylphosphonium tetrafluoroborate. , 20 mol%), 13 mL of tetralin, stir for 5 minutes.

Then, 22 mL of 3.0 M potassium phosphate aqueous solution was added to the four-necked flask, and the reaction solution was heated in an oil bath with a set temperature of 75° C. for 1 hour while stirring.

After the reaction solution was cooled, 100 mL of water and 100 mL of hexane were added, and then three liquid separation and washing were performed with water, and one liquid separation and washing was performed with a saturated sodium chloride aqueous solution.

The obtained solution was dried over anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 9.83 g (6.09 mmol, yield 91.7%) of compound 31 as a dark red oil.

The NMR spectrum of the obtained compound 31 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.46 (d, J _HH =5.2 Hz, 1H), 7.45 (d, J _HH =5.2 Hz, 1H), 7.07 (d, J _HH =5.2 Hz, 1H), 7.06 (d, J _HH =5.2 Hz, 1H), 7.02 (s, 1H), 6.98 (s, 1H), 6.86 (s, 1H), 6.84 (s, 1H), 2.19 (m, 4H), 1.91 (m , 4H), 1.73 (m, 4H), 1.18 (br, 120H), 0.86 (t, 18H).

<Synthesis Example 23> (Synthesis of Compound 32) Compound 32 represented by the following formula is synthesized from compound 31 represented by the following formula.

[Chemical 100]

In a 300 mL four-necked flask whose internal environment was replaced with nitrogen, 9.68 g (6.00 mmol) of compound 31 and 120 mL of chloroform were placed, and stirred at room temperature for 10 minutes to dissolve.

Next, 5.38 g (42.0 mmol) of (chloromethylene)dimethylammonium chloride was placed in a four-necked flask, and the mixture was heated in an oil bath with a set temperature of 65° C. for a total of 20 hours while stirring.

After the reaction solution was cooled, 100 mL of water was added, and the mixture was separated and washed twice with saturated sodium chloride aqueous solution.

The obtained solution was dried using anhydrous sodium sulfate and filtered, and then the solvent was distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 5.90 g (3.53 mmol, yield 58.9%) of compound 32 as purple oil.

The NMR spectrum of the obtained compound 32 was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 9.91 (s, 2H), 8.08 (s, 1H), 8.07 (s, 1H), 7.06 (s, 1H), 7.02 (s, 1H), 6.93 (s, 1H ), 6.91 (s, 1H), 2.22 (m, 4H), 1.92 (m, 4H), 1.75 (m, 4H), 1.21 (br, 120H), 0.85 (t, 18H).

<Synthesis Example 24> (Synthesis of Compound N-6) Compound N-6 represented by the following formula was synthesized using compound 32 represented by the following formula and compound 13.

[Chemistry 101]

In a 200 mL four-necked flask in which the internal environment was replaced with nitrogen, 2.25 g (1.35 mmol) of Compound 32, a compound synthesized by the method described in Adv. Mater. 2017, 29, 1703080. was placed. 13 0.888 g (3.38 mmol), 68 mL chloroform, 1.07 g (13.5 mmol) pyridine, heated in an oil bath at 65°C for 2 hours and stirred.

The obtained solution was cooled to normal temperature, and water was added to stop the reaction. After the obtained solution was extracted with chloroform, it was washed twice with water and once with a saturated sodium chloride aqueous solution.

Next, the obtained organic layer was dried using magnesium sulfate and filtered, and the solvent was further distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 1.91 g (0.886 mmol, yield 65.6%) of compound N-6 as a dark blue-green solid.

Regarding the obtained compound N-6, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 8.90 (s, 1H), 8.89 (s, 1H), 8.81 (s, 1H), 8.17 (s, 1H), 7.99 (s, 1H), 7.98 (s, 1H ), 7.11 (s, 1H), 7.07 (s, 1H), 6.98 (s, 1H), 6.98 (s, 1H), 2.25 (m, 4H), 1.94 (m, 4H), 1.77 (m, 4H) , 1.24 (br, 120H), 0.86 (m, 18H).

<Synthesis Example 25> (Synthesis of compound c) Compound c represented by the following formula was synthesized using 2-bromo-3-(2-ethylhexyl)thiophene (compound a) represented by the following formula and 2,5-dibromothiophene (compound b).

[Chemical 102]

In a 50 mL four-necked flask whose internal environment was replaced with nitrogen, 0.353 g (14.5 mmol) of magnesium, 10 mL of dehydrated diethyl ether, and a small amount of iodine were placed, and the flask was stirred at room temperature.

Next, put 2.00 g (7.27 mmol) of 2-bromo-3-(2-ethylhexyl)thiophene and 10 mL of dehydrated diethyl ether into the dropping funnel, and add dropwise to 50 mL while adjusting the dropping speed. in a four-necked flask so that the internal temperature becomes below 30°C.

Then, after heating and refluxing for 2 hours in an oil bath with a set temperature of 43°C, the reaction solution was cooled to normal temperature, and the obtained solution was used as a Grignard reaction solution.

In a 100 mL four-necked flask in which the internal environment was replaced with nitrogen, 1.76 g (7.27 mmol) of 2,5-dibromothiophene and [1,1'-bis(diphenylphosphino)diocene were placed Iron] palladium (II) dichloride 0.200 g (0.273 mmol), dehydrated diethyl ether 20 mL and stir.

After cooling in an ice-water bath, add the Grenya reaction solution dropwise into the 100 mL four-necked flask. After incubation for 2 hours, take out the 100 mL four-necked flask from the ice water bath, and warm the reaction solution to room temperature.

Next, 40 mL of water and 20 mL of heptane were added to the reaction solution, and liquid separation and washing were performed.

The obtained organic layer was dried using anhydrous magnesium sulfate and filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was purified using a silica gel column to obtain 1.48 g of compound c (4.14 mmol, yield 57.0%) as a yellow oil.

Regarding the obtained compound c, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.19 (d, J _HH =5.2 Hz, 1H), 7.00 (d, J _HH =3.9 Hz, 1H), 6.89 (d, J _HH =5.2 Hz, 1H), 6.84 (d, J _HH =3.9 Hz, 1H), 2.64 (d, J _HH =7.2 Hz, 2H), 1.62-1.51 (m, 1H), 1.33-1.16 (m, 8H), 0.90-0.80 (m, 6H ).

<Synthesis Example 26> (Synthesis of Compound e) Compound e represented by the following formula is synthesized using compound c represented by the following formula and compound d.

[Chemical 103]

In a 200 mL four-necked flask in which the internal environment was replaced with nitrogen, 1.46 g (4.09 mmol) of compound c and 1.42 g (1.78 mmol) of compound d synthesized by the method described in International Publication No. 2014/112656 were placed. , 59 mL of tetralin, and degassed by bubbling nitrogen for 30 minutes.

Then, in a four-necked flask, put 0.0813 g (dibenzylideneacetone) dipalladium (0) (0.0888 mmol, 5 mol%) and 0.103 g (0.355 mmol) tris-tert-butylphosphonium tetrafluoroborate. , 20 mol%), stir for 5 minutes.

Next, 5.9 mL of 3.0 M potassium phosphate aqueous solution was added to a four-necked flask, and the reaction solution was heated in an oil bath with a set temperature of 75° C. for 1 hour while stirring.

After the reaction solution was cooled, 103 mL of water and 103 mL of heptane were added to a four-necked flask. The organic layer was separated and washed three times with water and once with a saturated sodium chloride aqueous solution.

The obtained solution was dried using anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified using a silica gel column to obtain 1.81 g (1.67 mmol, yield 94.0%) of compound e as a red oil.

Regarding the obtained compound e, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 7.19-7.17 (m, 2H), 7.09 (d, J _HH =3.9 Hz, 1H), 7.07 (d, J _HH =3.9 Hz, 1H), 7.01 (d, J _HH =3.9 Hz, 2H), 6.92-6.90 (m, 2H), 6.78 (s, 1H), 6.76 (s, 1H), 2.72 (m, 4H), 1.95-1.81 (m, 4H), 1.68-1.64 (m, 2H), 1.42-1.23 (m, 56H), 0.91-0.83 (m, 18H).

<Synthesis Example 27> (Synthesis of Compound f) Compound f represented by the following formula is synthesized using compound e represented by the following formula.

[Chemical 104]

In a 100 mL four-necked flask in which the internal environment was replaced with nitrogen, 1.79 g (1.65 mmol) of compound e and 83 mL of methylene chloride were placed, and the compound e was dissolved by stirring at room temperature for 10 minutes.

Next, 0.845 g (6.60 mmol) of (chloromethylene)dimethylammonium chloride was placed in a four-necked flask, and the mixture was heated in an oil bath with a set temperature of 49° C. for 24 hours while stirring.

Then, after cooling the reaction solution, 13 mL of water was added, and the organic layer was separated and washed twice with a saturated sodium bicarbonate aqueous solution. The obtained solution was dried using anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified using a silica gel column to obtain 1.72 g of compound f (1.51 mmol, yield 91.4%) as a dark red oil.

Regarding the obtained compound f, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 9.84 (s, 2H), 7.56 (s, 1H), 7.55 (s, 1H), 7.19 (d, J _HH =3.9 Hz, 2H), 7.13 (d, J _HH =3.9 Hz, 1H), 7.11 (d, J _HH =3.9 Hz, 1H), 6.83 (s, 1H), 6.81 (s, 1H), 2.78-2.75 (m,4H), 1.96-1.82 (m, 4H ), 1.70-1.68 (m, 2H), 1.40-1.23 (m, 56H), 0.90-0.84 (m,18H).

<Synthesis Example 28> (Synthesis of Compound N-7) Compound N-7 represented by the following formula was synthesized using compound f and compound g represented by the following formula.

[Chemical 105]

In a 100 mL four-necked flask whose internal environment has been replaced with nitrogen, 0.798 g (0.700 mmol) of compound f, 0.442 g (1.68 mmol) of compound g, 35 mL of chloroform, and 0.554 g of pyridine (7.00 mmol) are placed, and the mixture is placed at 68 Heat in an oil bath at 1.5°C for 1.5 hours with stirring.

The obtained solution was cooled to normal temperature and added to 210 mL of methanol. The obtained solution was filtered to obtain a crude product as a precipitate.

The obtained crude product was purified using a silica gel column to obtain 0.981 g (0.602 mmol, yield 86.0%) of compound N-7 as a black solid.

Regarding the obtained compound N-7, the NMR spectrum was analyzed. The results are as follows. [ ¹ H NMR (CDCl ₃ )] δ 8.69 (s, 1H), 8.68 (s, 1H), 8.67 (s, 2H), 7.89 (s, 1H), 7.88 (s, 1H), 7.54 (s, 1H ), 7.53 (s, 1H), 7.38 (d, J _HH =4.1 Hz, 1H), 7.36 (d, J _HH =4.0 Hz, 1H), 7.08 (d, J _HH =4.3 Hz, 1H), 7.05 ( d, J _HH =4.0 Hz, 1H),6.85 (s, 1H),6.80 (s, 1H), 2.76-2.72(m,4H), 1.96-1.92 (m, 4H), 1.74 (br, 2H), 1.41-1.23 (m, 56H), 0.95-0.83 (m, 18H).

<Preparation Example 1> (Preparation of Ink I-1) Tetralin was used as the first solvent, butyl benzoate was used as the second solvent, and the volume ratio of the first solvent and the second solvent was set to 97:3 to prepare a mixed solvent. In the prepared mixed solvent, the polymer compound P-1 as a p-type semiconductor material was contained at a concentration of 1.2 mass % with respect to the total mass of the ink, and the compound N-1 as an n-type semiconductor material was The mixture was mixed at a concentration of 1.2% by mass (p-type semiconductor material/n-type semiconductor material = 1/1) based on the total mass of the ink, and stirred at 60° C. for 8 hours to obtain a mixed liquid. The mixed liquid was filtered using a filter, and ink (I-1) was obtained.

<Preparation Example 2 to Preparation Example 17> (Preparation of Ink I-2 to Ink I-17) Ink (I-2) to ink (I-17) were obtained in the same manner as in Preparation Example 1, except that the solvent and the n-type semiconductor material were used in the combination shown in Table 9 below.

[Table 9] (Table 9) ink n-type semiconductor material First solvent (S1) Second solvent (S2) |P( ^B1 )-P(S2)| (Unit: MPa ^0.5 ) Preparation Example 1 I-1 N-1 Tetralin Butyl benzoate 3.9 Preparation Example 2 I-2 N-1 pseudocumene 1,2-Dimethoxybenzene 1.2 Preparation Example 3 I-3 N-2 o-xylene Methyl benzoate 6.8 Preparation Example 4 I-4 N-2 pseudocumene 1,2-Dimethoxybenzene 3.2 Preparation Example 5 I-5 N-2 o-dichlorobenzene - - Preparation Example 6 I-6 N-3 o-xylene Acetophenone 7.4 Preparation Example 7 I-7 N-3 Tetralin Butyl benzoate 4.0 Preparation Example 8 I-8 N-3 Tetralin - - Preparation Example 9 I-9 N-4 o-xylene Methyl benzoate 6.0 Preparation Example 10 I-10 N-4 Tetralin - - Preparation Example 11 I-11 N-5 pseudocumene 1,2-Dimethoxybenzene 3.3 Preparation Example 12 I-12 N-5 o-xylene Methyl benzoate 7.1 Preparation Example 13 I-13 N-5 o-xylene - - Preparation Example 14 I-14 N-6 Tetralin Butyl benzoate 3.0 Preparation Example 15 I-15 N-6 o-Dichlorobenzene - - Preparation Example 16 I-16 N-7 o-xylene Methyl benzoate 7.3 Preparation Example 17 I-17 N-7 Tetralin - -

<Example 1> (Production and evaluation of photoelectric conversion element) (1) Manufacturing of photoelectric conversion components and their sealed bodies A glass substrate on which a thin film (anode) of ITO was formed to a thickness of 50 nm by a sputtering method was prepared, and ozone UV treatment was performed on the glass substrate as a surface treatment.

Next, the ink (I-1) is applied on the thin film of ITO by spin coating to form a coating film, and then it is heated for 10 minutes using a hot plate heated to 100°C in a nitrogen atmosphere to dry it and form an active layer. layer. The thickness of the active layer formed is approximately 300 nm.

Next, ZnO (manufactured by Tayca, product name: HTD-711Z) was coated on the formed active layer by a spin coating method to form an electron transport layer with a thickness of approximately 50 nm.

Then, a silver (Ag) layer was formed with a thickness of about 60 nm on the formed electron transport layer as a cathode. Through the above steps, a photoelectric conversion element is manufactured on the glass substrate.

Next, a UV curable sealant as a sealing material is applied to the glass substrate as the supporting substrate so as to surround the periphery of the produced photoelectric conversion element, and the glass substrate as the sealing substrate is bonded, and then UV light is irradiated. The photoelectric conversion element is sealed in the gap between the supporting substrate and the sealing substrate, thereby obtaining a sealed body of the photoelectric conversion element. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate is a square of 2 mm × 2 mm when viewed in the thickness direction. The obtained sealed body was designated as Sample 1.

(2) Evaluation of photoelectric conversion elements (evaluation of external quantum efficiency) A reverse bias voltage of -5 V was applied to the manufactured sample 1, and the external quantum efficiency (EQE) at a wavelength of 940 nm under the applied voltage was measured using a spectrophotometric sensitivity measuring device (CEP-2000, manufactured by Spectrometer Co., Ltd.). Measure and evaluate.

＜Comparative example 1＞ A photoelectric conversion element was produced and evaluated in the same manner as in Example 1 except that ink (I-2) was used.

＜Evaluation 1＞ The relative percentage (EQE relative value, unit: %) of the EQE of the photoelectric conversion element of Example 1 to the EQE of the photoelectric conversion element of Comparative Example 1 was found to be 122%. That is, the EQE of the photoelectric conversion element of Example 1 is higher than the EQE of the photoelectric conversion element of Comparative Example 1. The results are also shown in Table 10 below.

<Example 2, Comparative Example 2, Reference Example 1> The photoelectric conversion element was produced and evaluated in the same manner as in Example 1, except that ink (I-3), ink (I-4), and ink (I-5) were used respectively.

＜Evaluation 2＞ Compared with the EQE value of the photoelectric conversion element of Reference Example 1, the relative EQE value of the photoelectric conversion element obtained in Example 1 was 118%, and the relative EQE value of the photoelectric conversion element of Comparative Example 1 was 94%. It is known that excellent EQE characteristics can be obtained in Example 2 although the compounds used as n-type semiconductor materials are all compounds N-2. The results are also shown in Table 10 below.

<Example 3 to Example 8, Comparative Example 3, and Reference Example 2 to Reference Example 6> Using the photoelectric conversion elements produced using ink (I-6) to ink (I-17), comparisons were made between Examples and Comparative Examples with respect to the Reference Example in the same manner as described above. The results are also shown in Table 10 below.

[Table 10] (Table 10) ink EQE relative value (%) Example 1 I-1 122 Comparative example 1 I-2 100 Example 2 I-3 118 Comparative example 2 I-4 94 Base case 1 I-5 100 Example 3 I-6 133 Example 4 I-7 137 Base case 2 I-8 100 Example 5 I-9 170 Base case 3 I-10 100 Example 6 I-11 230 Example 7 I-12 160 Base case 4 I-13 100 Comparative example 3 I-14 91 Base example 5 I-15 100 Example 8 I-16 138 Base example 6 I-17 100

As shown in Table 10, the photoelectric conversion element was produced by using an ink composition that satisfied the requirements of the present invention as the ink composition for forming the active layer, and the photoelectric conversion element was produced by using an ink composition that did not meet the requirements of the present invention. Compared with photoelectric conversion elements, EQE can be improved.

10: Photoelectric conversion element 11, 210: Support substrate 12:Anode 13: Hole transport layer 14:Active layer 15:Electron transport layer 16:Cathode 17:Sealing components

FIG. 1 is a diagram schematically showing a structural example of a photoelectric conversion element.

10: Photoelectric conversion element

11:Support substrate

12:Anode

13: Hole transport layer

14:Active layer

15:Electron transport layer

16:Cathode

17:Sealing components

Claims (12)

An ink composition comprising: a semiconductor material, including at least one p-type semiconductor material and at least one n-type semiconductor material; and two or more solvents, including a first solvent and a solvent having a boiling point higher than that of the first solvent. The second solvent with a boiling point, any one of the p-type semiconductor material and the n-type semiconductor material is a non-fullerene compound represented by the following formula (I), Hansen solubility parameter of the compound containing B ¹ The polar term P (B ¹ ) (MPa ^0.5 ) and the polar term P (S2) (MPa ^0.5 ) of the Hansen solubility parameter of the second solvent satisfy the conditions represented by the following formula (III), and the B ¹ The terminal formed by cutting the bond between A ¹ and B ¹ in the non-fullerene compound represented by the following formula (I) is terminated with a hydrogen atom; A ¹ -B ¹ -(A ¹ )n (I ) |P(B ¹ )-P(S2)|＞3.2(MPa ^0.5 ) (III) In formula (I), A ¹ represents an electron-withdrawing group, and B ¹ represents one or more structural units and constitutes π A conjugated group, n is 0 or 1. When n is 1, the two A ^1's may be the same or different, including terminal hydrogen atoms formed by cutting the bond between A ¹ and B ¹ The compound of blocked A ¹ and the compound containing B ¹ satisfy the conditions represented by the following formula (II); E _HOMO (B ¹ )-E _HOMO (A ¹ )>2.0 (eV) (II) In formula (II) , E _HOMO (B ¹ ) (eV) represents the value of the energy level of the highest occupied orbital of a compound containing B ¹ whose terminal is terminated with a hydrogen atom, which is formed by cutting the bond between A ¹ and B ¹ , E _HOMO (A ¹ ) (eV) represents the value of the energy level of the highest occupied orbital of a compound containing A ¹ whose terminal is terminated with a hydrogen atom, which is formed by cutting the bond between A ¹ and B ¹ . The ink composition according to claim 1, wherein the second solvent is a solvent having a boiling point that is 30° C. or more higher than the boiling point of the first solvent. The ink composition according to claim 1 or 2, wherein the second solvent is an ether solvent, an aromatic hydrocarbon solvent, a ketone solvent or an ester solvent. The ink composition according to any one of claims 1 to 3, wherein the non-fullerene compound represented by the formula (I) is an n-type semiconductor material. The ink composition according to any one of claims 1 to 4, wherein in the formula (I), the first structural unit is at least one of the one or more structural units contained in B ¹ It is a structural unit represented by the following formula (IV), and the remaining second structural unit other than the first structural unit is a divalent group containing an unsaturated bond, a divalent aromatic carbocyclic group or a divalent aromatic group. Heterocyclyl group, when there are two or more first structural units, the two or more first structural units may be the same or different, and when there are two or more second structural units, there Two or more second structural units may be the same or different; In the formula (IV), Ar ¹ and Ar ² each independently represent an aromatic carbocyclic ring that may have a substituent or an aromatic heterocyclic ring that may have a substituent, Y represents a direct bond, and -C(=O)- represents of a group or an oxygen atom, R independently represents: 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 alkyl group that may have a substituent Oxy group, optionally substituted cycloalkyloxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted cycloalkylthio group, optionally substituted arylthio group group, a monovalent heterocyclic group that may have a substituent, a substituted amine group that may have a substituent, a acyl group that may have a substituent, an imine residue that may have a substituent, a amide group that may have a substituent, amide group having a substituent, a substituted oxycarbonyl group that may have a substituent, an alkenyl group that may have a substituent, a cycloalkenyl group that may have a substituent, an alkynyl group that may have a substituent, a ring that may have a substituent Alkynyl group, cyano group, nitro group, a group represented by -C(=O)-R ^a , or a group represented by -SO ₂ -R ^b , R ^a and R ^b each independently represent: a hydrogen atom, which may have An alkyl group that may have a substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, an aryloxy group that may have a substituent, or a monovalent heterocyclic group that may have a substituent; there are multiple R may be the same as or different from each other. The ink composition according to claim 5, wherein the first structural unit is a structural unit represented by the following formula (V); In the formula (V), Y and R are as defined above, X ¹ and X ² each independently represent a sulfur atom or an oxygen atom, and Z ¹ and Z ² each independently represent a group represented by =C(R)- or Nitrogen atom. The ink composition according to claim 6, wherein the first structural unit is a structural unit represented by the following formula (V-1); In formula (V-1), Y represents a group represented by -C(=O)- or an oxygen atom, and R each independently represents: a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkyl group that may have a substituent Cycloalkyl group, aryl group which may have a substituent, alkyloxy group which may have a substituent, cycloalkyloxy group which may have a substituent, aryloxy group which may have a substituent, alkylthio which may have a substituent group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, a hydroxyl group which may have a substituent, Imine residue having a substituent, amide group which may have a substituent, amide group which may have a substituent, substituted oxycarbonyl group which may have a substituent, alkenyl group which may have a substituent, alkenyl group which may have a substituent a cycloalkenyl group, an alkynyl group that may have a substituent, a cycloalkynyl group that may have a substituent, a cyano group, a nitro group, a group represented by -C(=O)-R ^a , or a group represented by -SO ₂ -R ^b The groups represented, R ^a and R ^b each independently represent: a hydrogen 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 aryl group which may have a substituent An oxygen group, or a monovalent heterocyclic group which may have a substituent; the plural R present may be the same or different. The ink composition according to claim 6 or 7, wherein B ¹ has any one structure selected from the group consisting of the structures represented by the following formula (VII-1) to formula (VII-16) Bivalent base; -CU1- (VII-1) -CU1-CU1- (VII-2) -CU1-CU2- (VII-3) -CU1-CU1-CU1- (VII-4) -CU1-CU2-CU1 - (VII-5) -CU1-CU1-CU2- (VII-6) -CU1-CU2-CU2- (VII-7) -CU2-CU1-CU2- (VII-8) -CU1-CU1-CU1-CU1 - (VII-9) -CU1-CU1-CU1-CU2- (VII-10) -CU1-CU1-CU2-CU1- (VII-11) -CU1-CU1-CU2-CU2- (VII-12) -CU1 -CU2-CU1-CU2- (VII-13) -CU1-CU2-CU2-CU1- (VII-14) -CU1-CU2-CU2-CU2- (VII-15) -CU2-CU1-CU2-CU2- ( VII-16) In formulas (VII-1) to (VII-16), CU1 represents the first structural unit, and CU2 represents the second structural unit; when there are two or more CU1s, there are two The above CU1 may be the same or different. When there are two or more CU2s, the two or more CU2s may be the same or different. The ink composition according to any one of claims 1 to 8, wherein the p-type semiconductor material is a conjugated polymer compound. A cured film obtained by curing the ink composition according to any one of claims 1 to 9. A photoelectric conversion element includes a first electrode, a second electrode, and an active layer disposed between the first electrode and the second electrode. The active layer is the cured film according to claim 10. The photoelectric conversion element according to claim 11 is a photodetection element.