JP2021127398A - Polymer, composition, ink, and photoelectric conversion element - Google Patents

Abstract

To provide a polymer compound which, when used in a photoelectric conversion element, renders high EQE possible in a given range of wavelengths not shorter than 1,000 nm.SOLUTION: A polymer compound comprises a constituent unit represented by a formula (1) and a constituent unit represented by a formula (2). (In the formulae, X1 and X2 each independently represent a sulfur atom or an oxygen atom, Z represents a nitrogen atom or a group represented by -C(Ra)=, and R1, R2, R3, and Ra independently represent H, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or the like).SELECTED DRAWING: Figure 1

Description

The present invention relates to polymeric compounds, compositions, inks, and photoelectric conversion elements.

The photoelectric conversion element is attracting attention because it is an extremely useful device from the viewpoint of energy saving and reduction of carbon dioxide emissions, for example.

As the electron donating compound used in the photoelectric conversion element, for example, the following polymer compounds are known (Patent Document 1: Polymer 1, Non-Patent Document 1).

In the polymer 1, R ¹ represents 2-ethylhexyl. R ² represents 3,7-dimethyloctyl.

JP-A-2015-172131

Macromolecules, 2013, 46 (9), 3384-3390

In recent years, there has been an increasing demand for devices such as image sensors and biometric authentication devices that detect infrared rays. The photoelectric conversion element used in these devices is required to be able to efficiently convert light in a predetermined wavelength range having a wavelength of 1000 nm or more into an electric signal, depending on the type of each device.

However, a general-purpose photoelectric conversion element using an inorganic semiconductor such as silicon usually has an external quantum efficiency (EQE) of several percent or less for light having a wavelength of 1000 nm or more. Among the photoelectric conversion elements using special inorganic semiconductors, there are elements having a relatively high EQE for light having a wavelength of 1000 nm or more, but the manufacturing cost is high.
On the other hand, a photoelectric conversion element using an organic polymer compound generally has a lower manufacturing cost than a photoelectric conversion element using an inorganic semiconductor. However, the photoelectric conversion element using the organic polymer compound described in Patent Document 1 and Non-Patent Document 1 has a very small EQE for light having a wavelength of 1000 nm or more.

Therefore, there is a need for a polymer compound capable of achieving high EQE in a predetermined wavelength range of 1000 nm or more when used in a photoelectric conversion element.

As a result of diligent studies to solve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved by a polymer compound containing a specific structural unit, and has completed the present invention.
That is, the present invention provides the following.

（式中、
Ｘ^１及びＸ^２は、それぞれ独立して、硫黄原子又は酸素原子を表し、
Ｚは、窒素原子、又は、−Ｃ（Ｒ^ａ）＝で表される基を表し、
Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^ａは、それぞれ独立して、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい１価の複素環基、
−Ｃ（＝Ｏ）−Ｒ^ｂで表される基、又は
−ＳＯ_２−Ｒ^ｃで表される基を表し、
Ｒ^ｂ及びＲ^ｃは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい１価の複素環基を表す。）
［２］ 式（１）で表される構成単位と、式（２）で表される構成単位とが、直接結合した単位を含む、［１］に記載の高分子化合物。
［３］ 構成単位が、式（１）で表される構成単位及び式（２）で表される構成単位のみからなる、［１］又は［２］に記載の高分子化合物。
［４］ Ｚが、窒素原子である、［１］〜［３］のいずれか一項に記載の高分子化合物。
［５］ Ｘ^１及びＸ^２が、それぞれ硫黄原子である、［１］〜［４］のいずれか一項に記載の高分子化合物。
［６］ Ｒ^１、Ｒ^２、及びＲ^３が、それぞれ独立して、置換基を有していてもよいアルキル基である、［１］〜［５］のいずれか一項に記載の高分子化合物。
［７］ ［１］〜［６］のいずれか一項に記載の高分子化合物と、ｎ型半導体材料とを含む、組成物。
［８］ ［１］〜［６］のいずれか一項に記載の高分子化合物と、ｎ型半導体材料と、溶媒とを含む、インク。
［９］ ［１］〜［６］のいずれか一項に記載の高分子化合物を含む、光電変換素子。
［１０］ 光検出素子である、［９］に記載の光電変換素子。
［１１］ ［９］又は［１０］に記載の光電変換素子を含む、イメージセンサ。
［１２］ ［９］又は［１０］に記載の光電変換素子を含む、生体認証装置。 [1] A polymer compound containing a structural unit represented by the formula (1) and a structural unit represented by the formula (2).

(During the ceremony,
X ¹ and X ² independently represent a sulfur atom or an oxygen atom, respectively.
Z represents a nitrogen atom or a group represented by ^{−C (Ra) =.
R 1, R 2, R 3} , and ^{R a} are each independently,
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
Cycloalkynyl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Aryl groups that may have substituents,
Aryloxy groups, which may have substituents,
Arylthio groups, which may have substituents,
A monovalent heterocyclic group which may have a substituent,
Represents a group represented by -C (= O) -R ^b or a group represented by -SO _2- R ^c .
R ^b and R ^c are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Aryl groups that may have substituents,
Alkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent. )
[2] The polymer compound according to [1], which comprises a unit in which the structural unit represented by the formula (1) and the structural unit represented by the formula (2) are directly bonded.
[3] The polymer compound according to [1] or [2], wherein the structural unit comprises only the structural unit represented by the formula (1) and the structural unit represented by the formula (2).
[4] The polymer compound according to any one of [1] to [3], wherein Z is a nitrogen atom.
[5] The polymer compound according to any one of [1] to [4], wherein ^{X 1} and X ^{2 are sulfur atoms, respectively.}
[6] The polymer according to any one of [1] to [5], wherein ^{R 1} , R ^{2 and R 3 are alkyl groups which may independently have a substituent.} Compound.
[7] A composition containing the polymer compound according to any one of [1] to [6] and an n-type semiconductor material.
[8] An ink containing the polymer compound according to any one of [1] to [6], an n-type semiconductor material, and a solvent.
[9] A photoelectric conversion element containing the polymer compound according to any one of [1] to [6].
[10] The photoelectric conversion element according to [9], which is an optical detection element.
[11] An image sensor including the photoelectric conversion element according to [9] or [10].
[12] A biometric authentication device including the photoelectric conversion element according to [9] or [10].

According to the present invention, a polymer compound capable of achieving high EQE in a predetermined wavelength range of 1000 nm or more when used in a photoelectric conversion element; a composition containing the polymer compound; an ink containing the polymer compound. A photoelectric conversion element containing the polymer compound; can be provided.

FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element. FIG. 2 is a diagram schematically showing a configuration example of an image detection unit. FIG. 3 is a diagram schematically showing a configuration example of the fingerprint detection unit.

[Explanation of terms]
Hereinafter, terms in the present specification will be described.
The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ or more and 1 × ¹⁰⁸ or less. The structural units contained in the polymer compound are 100 mol% in total.

The “constituent unit” means a residue derived from a raw material monomer, which is present at least one in the polymer compound.

The "hydrogen atom" may be a light hydrogen atom or a deuterium atom.

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

In the "may have substituents" embodiment, all hydrogen atoms constituting the compound or group are unsubstituted, and some or all of one or more hydrogen atoms are substituted with substituents. Both aspects, if any, are included.

Examples of substituents 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, Examples thereof include an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acidimide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. ..

The "alkyl group" may be linear or branched. The alkyl group may have a substituent. The number of carbon atoms of the alkyl group is usually 1 to 30, not including the number of carbon atoms of the substituent.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl grave, n-pentyl group, isopentyl group, 2-. Methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 2-ethylhexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 4,4-dimethylpentyl group, heptyl group, Octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, 3,7,11-trimethyldodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, An icosyl group can be mentioned.

Examples of alkyl groups having substituents are alkyl groups in which one or more hydrogen atoms are substituted with fluorine atoms (eg, trifluoromethyl group, pentafluoroethyl group, 4,4,4, -trifluorobutyl group). , -CH _2- (CF ₂ ) _{2- CF 3} group,-(CF ₂ ) _2- CH _{2- CF 3} group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl Group), an alkyl group in which one or more hydrogen atoms are substituted with a chlorine atom (eg, a trichloromethyl group, a 4,4,4-trichlorobutyl group), an alkyl group substituted with an alkyloxy group, or an aryl group. Alkyl groups that have been added can be mentioned.

The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms of the cycloalkyl group is usually 3 to 30, not including the number of carbon atoms of the substituent. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.

Examples of cycloalkyl groups having a substituent include a cycloalkyl group in which one or more hydrogen atoms are substituted with a fluorine atom, a cycloalkyl group substituted with an alkyl group, and a cycloalkyl group substituted with an alkyloxy group. Can be mentioned.

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

Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group and a 5-hexenyl group. , 7-octenyl group.

Examples of the alkenyl group having a substituent include an alkenyl group in which one or more hydrogen atoms are substituted with a fluorine atom, and an alkenyl group in which one or more hydrogen atoms are substituted with a C1 to C12 alkyloxy group. "C1 to C12 alkyl" indicates that the number of carbon atoms is 1 to 12. Further, "Cm to Cn alkyl" indicates that the number of carbon atoms is m to n. The same applies to the following.

The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group is usually 3 to 30, not including the number of carbon atoms of the substituent.

Specific examples of the cycloalkenyl group include a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

Examples of cycloalkenyl groups having substituents include cycloalkenyl groups in which one or more hydrogen atoms are substituted with fluorine atoms, cycloalkenyl groups substituted with C1-C12 alkyl groups, and C1-C12 alkyloxy groups. Cycloalkenyl groups that have been added can be mentioned.

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

Specific examples of the alkynyl group include 1-ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-methyl-1-butynyl group, 3-pentynyl group and 4-pentynyl. Groups include 1-hexynyl group, 5-hexynyl group and 7-octynyl group.

Examples of the alkynyl group having a substituent include an alkynyl group in which one or more hydrogen atoms are substituted with a fluorine atom, and an alkynyl group in which one or more hydrogen atoms are substituted with a C1 to C12 alkyloxy group.

The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms of the cycloalkynyl group is usually 3 to 30, not including the number of carbon atoms of the substituent.
Specific examples of the cycloalkynyl group include a cyclopentynyl group, a cyclohexynyl group, a cycloheptinyl group, and a cyclooctynyl group.

Examples of cycloalkynyl groups having substituents include cycloalkynyl groups in which one or more hydrogen atoms are substituted with fluorine atoms, cycloalkynyl groups substituted with C1-C12 alkyl groups, and C1-C12 alkyloxy groups. Cycloalkynyl groups that have been used can be mentioned.

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

Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group and a heptyloxy group. , Octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, 3,7,11-trimethyldodecyloxy group.

Examples of alkyloxy groups having substituents include alkyloxy groups in which one or more hydrogen atoms are substituted with fluorine atoms (eg, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyloxy). Groups, perfluorooctyloxy groups), alkyloxy groups substituted with alkyloxy groups (eg, methoxymethyloxy groups, 2-methoxyethyloxy groups).

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 is usually 3 to 30, not including the number of carbon atoms of the substituent.

Specific examples of the cycloalkyloxy group include a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group.

Examples of the cycloalkyl group having a substituent include a cycloalkyloxy group in which one or more hydrogen atoms are substituted with a fluorine atom, and a cycloalkyloxy group in which one or more hydrogen atoms are substituted with a C1 to C12 alkyl group.

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

Specific examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, 2 Examples thereof include a-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group and a dodecylthio group.

Examples of alkylthio groups having a substituent include a trifluoromethylthio group.

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 is usually 3 to 30, not including the number of carbon atoms of the substituent.

Specific examples of the cycloalkylthio group include a cyclopentylthio group, a cyclohexylthio group, and a cycloheptylthio group.

Examples of the cycloalkylthio group having a substituent include a cycloalkylthio group in which one or more hydrogen atoms are substituted with a fluorine atom, and a cycloalkylthio group in which one or more hydrogen atoms are substituted with a C1 to C12 alkyl group.

The "aryl group" means the remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon which may have a substituent. Therefore, the aryl group may have a substituent.

The number of carbon atoms of the aryl group is usually 6 to 60, not including the number of carbon atoms of the substituent.
Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-pyrenyl group, a 2-pyrenyl group, and a 4-pyrenyl group. , 2-Fluorenyl group, 3-Fluorenyl group, 4-Fluorenyl group, 2-Phenylphenyl group, 3-Phenylphenyl group, 4-Phenylphenyl group.

Examples of an aryl group having a substituent include an aryl group in which one or more hydrogen atoms are substituted with a fluorine atom (eg, a pentafluorophenyl group), and an aryl group in which one or more hydrogen atoms are substituted with a chlorine atom. (Example, 3,4,5-trichlorophenyl), C1-C12 alkyloxyphenyl group, C1-C12 alkylphenyl group, C1-C12 alkylsulfonylphenyl group, cyanophenyl group can be mentioned.

The "aryloxy group" may have a substituent. The number of carbon atoms of the aryloxy group is usually 6 to 60, not including the number of carbon atoms of the substituent.

Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthryloxy group, a 9-anthryloxy group, and a 1-pyrenyloxy group.

Examples of the aryloxy group having a substituent include a C1-C12 alkyloxyphenoxy group, a C1-C12 alkylphenoxy group, and a pentafluorophenyloxy group.

The "arylthio group" may have a substituent. The number of carbon atoms of the arylthio group is usually 6 to 60, not including the number of carbon atoms of the substituent.

Specific examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

Specific examples of the arylthio group having a substituent include a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, and a pentafluorophenylthio group.

The "monovalent heterocyclic group" means the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the ring from the heterocyclic compound which may have a substituent. Therefore, the monovalent heterocyclic group may have a substituent.

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

Examples of heterocyclic compounds for constructing a monovalent heterocyclic group include furan, thiophene, pyrrol, pyrrolin, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline. , Prazolysin, Frazan, Triazole, Thiasiazol, Oxazole, Tetrazole, Pyran, pyridine, Piperidine, Thiopirane, Pyridazine, Pyrimidine, Pyrazine, Piperazine, Morpholine, Triazin, Benzofuran, Isobenzofuran, Benzothiophene, Indol, Isoindole, Indridin , Indolin, Isoindrin, Chromen, Chroman, Isochroman, Benzopyran, Kinolin, Isoquinoline, Kinolidine, Benzoimidazole, Benzothiazole, Indazole, Naftilidine, Kinoxalin, Kinazoline, Kinazolidine, Synnoline, Phthalazine, Purine, Pteridine, Carbazole, Xanthene, Phenant Examples thereof include lysine, aclysine, β-carbolin, perimidine, phenanthroline, thianthrane, phenoxatiin, phenoxazine, phenothiazine and phenazine.

Specific examples of the monovalent heterocyclic group include a thienyl group, a thiazolyl group, an oxazolyl group, a pyrrolyl group, a frill group, a pyridyl group, a pyrazil group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group and a triazinyl group. ..

As an example of a monovalent heterocyclic group having a substituent, a monovalent heterocyclic group in which one or more hydrogen atoms are substituted with C1 to C12 alkyl groups, and one or more hydrogen atoms are C1 to C12 alkyloxy. Examples include monovalent heterocyclic groups substituted with groups.

"Substituent amino group" means an amino group having a substituent. As the substituent contained in the amino group, an alkyl group, an aryl group and a monovalent heterocyclic group are preferable. The number of carbon atoms of the substituted amino group is usually 1 to 30, not including the number of carbon atoms of the substituent.
Examples of substituted amino groups include dialkylamino groups (eg, dimethylamino group, diethylamino group), diarylamino groups (eg, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl). ) Amino group, bis (3,5-di-tert-butylphenyl) amino group).

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

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

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

The "amide group" means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the 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 formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group and dibenzamide group. , Ditrifluoroacetamide group, and dipentafluorobenzamide group.

The "acidimide group" means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the acidimide. The number of carbon atoms of the acidimide group is usually 4 to 20. Specific examples of the acidimide group include a group represented by the following structural formula.

The "substituted oxycarbonyl group" means a group represented by R'-O- (C = O)-. Here, R'represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, which may have a substituent.

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

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

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

[1. Polymer compound]
The polymer compound according to one embodiment of the present invention includes a structural unit represented by the formula (1) and a structural unit represented by the formula (2). The structural unit represented by the formula (1) and the structural unit represented by the formula (2) are divalent groups. Hereinafter, the polymer compound according to the embodiment of the present invention is also referred to as a polymer compound P.

Each symbol in the formula has the following meaning. The meanings and examples of the symbols below can be freely combined with each other.

X ¹ and X ² independently represent a sulfur atom or an oxygen atom. Preferably, X ¹ and X ² are sulfur atoms, respectively.

Z represents a nitrogen atom or ^{a group represented by −C (Ra} ) =, and is preferably a nitrogen atom.

^{R 1, R 2, R 3} , and R ^a are each independently hydrogen atom, a halogen atom, an optionally substituted alkyl group, which may have a substituent cycloalkyl group, An alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, An alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, An arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a group ^{represented by -C (= O) -R b} , or -SO _2- R ^c. Represents a group represented by.

R ^b and R ^c are independently hydrogen atoms, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkyloxy which may have a substituent. It represents a group, an aryloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent.

Halogen atom represented by ^{R 1, R 2, R 3} , and ^{R a} is preferably a fluorine atom.

^{R 1, R 2, R 3} , and alkyl group which may have a substituent represented by R ^a may preferably have a substituent, an alkyl having 1 to 20 carbon atoms It is a group, more preferably an alkyl group having 1 to 15 carbon atoms, which may have a substituent, and more preferably an alkyl group having 1 to 12 carbon atoms, which may have a substituent. It is an alkyl group of 1 to 10, more preferably an alkyl group having 1 to 10 carbon atoms, which may have a substituent. Here, the number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and Examples of the substituent that the alkyl group have represented by R ^a is preferably a halogen atom, more preferably a fluorine atom and / or chlorine atoms.

^{R 1, R 2, R 3} , and cycloalkyl group which may have a substituent represented by R ^a may preferably have a substituent, a C 3-10 carbon atoms It is a cycloalkyl group, more preferably a cycloalkyl group having 5 to 6 carbon atoms, which may have a substituent, and more preferably a cyclohexyl group, which may have a substituent. be. Here, the number of carbon atoms of the cycloalkyl group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and an alkenyl group optionally having a substituent represented by R ^a may preferably have a substituent, an alkenyl having 2 to 10 carbon atoms It is a group, more preferably an alkenyl group having 2 to 6 carbon atoms, which may have a substituent, and more preferably a 2-propenyl group or 5 which may have a substituent. -Hexenyl group. Here, the number of carbon atoms of the alkenyl group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and substituents may cycloalkenyl group which may have a represented by R ^a may preferably have a substituent, a C 3-10 carbon atoms It is a cycloalkenyl group, more preferably a cycloalkenyl group having 6 to 7 carbon atoms, which may have a substituent, and more preferably a cyclohexenyl group which may have a substituent. Or it is a cycloheptenyl group. Here, the number of carbon atoms of the cycloalkenyl group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and substituents may have a cycloalkenyl group represented by ^{R a} preferably is C1~C12 alkyl group.

^{R 1, R 2, R 3} , and alkynyl which may have a substituent represented by R ^a may preferably have a substituent, an alkynyl having 2 to 10 carbon atoms It is a group, more preferably an alkynyl group having 5 to 6 carbon atoms, which may have a substituent, and more preferably a 5-hexynyl group or 3 which may have a substituent. -Methyl-1-butynyl group. Here, the number of carbon atoms of the alkynyl group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and R ^a good cycloalkynyl group which may have a substituent represented by may preferably have a substituent group, of 6 to 10 carbon atoms It is a cycloalkynyl group, more preferably a cycloalkynyl group having 7 to 8 carbon atoms which may have a substituent, and even more preferably a cycloheptinyl group or which may have a substituent. It is a cyclooctynyl group. Here, the number of carbon atoms of the cycloalkynyl group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and substituents which may be possessed by cycloalkynyl group represented by ^{R a} preferably is C1~C12 alkyl group.

^{R 1, R 2, R 3} , and alkyl group which may have a substituent represented by R ^a preferably may have a substituent group, having 1 to 10 carbon atoms It is an alkyloxy group, more preferably an alkyloxy group having 1 to 8 carbon atoms, which may have a substituent, and more preferably a methoxy group, an ethoxy group, a propyloxy group, or 3-methyl. It is a butyloxy or 2-ethylhexyloxy group, and these groups may have a substituent. Here, the number of carbon atoms of the alkyloxy group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and alkylthio group which may have a substituent represented by R ^a may preferably have a substituent, alkylthio of 1 to 6 carbon atoms It is a group, more preferably an alkylthio group having 1 to 3 carbon atoms, which may have a substituent, and more preferably a methylthio group or a propylthio group, which may have a substituent. be. Here, the number of carbon atoms of the alkylthio group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and an aryl group which may have a substituent represented by R ^a may preferably have a substituent, an aryl having 6 to 15 carbon atoms It is a group, more preferably a phenyl group or a naphthyl group which may have a substituent. Here, the number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and substituents may be aryl groups have represented by ^{R a} preferably include a halogen atom (e.g., chlorine atom, fluorine atom), Cl -C 12 alkyl group ( Examples, methyl group, trifluoromethyl group, tert-butyl group, octyl group, dodecyl group), C1-C12 alkyloxy group (eg, methoxy group, ethoxy group, octyloxy group), C1-C12 alkylsulfonyl group (eg) , Dodecylsulfonyl group), and / or a cyano group.

^{R 1, R 2, R 3} , and an aryloxy group optionally having a substituent represented by R ^a may preferably have a substituent group, the number 6 to 15 carbon atoms It is an aryloxy group, more preferably a phenyloxy group or an anthrasenyloxy group which may have a substituent. Here, the number of carbon atoms of the aryloxy group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and the substituent which may be an aryloxy group have represented by ^{R a} is preferably a C1~C12 alkyl group, more preferably C1~C6 alkyl group Yes, more preferably a methyl group.

^{R 1, R 2, R 3} , and optionally arylthio group optionally having a substituent represented by R ^a may preferably have a substituent, an arylthio of 6 to 10 carbon atoms It is a group, more preferably a phenylthio group which may have a substituent. Here, the number of carbon atoms of the arylthio group does not include the number of carbon atoms of the substituent.

^{R 1, R 2, R 3} , and the substituent which may be arylthio group have represented by ^{R a} is preferably a C1~C12 alkyl group, more preferably be a C1~C6 alkyl group , More preferably a methyl group.
NS.

R ^{1, R} 2, ^{R 3,} and the heterocyclic group of monovalent which may have a substituent represented by R ^a may preferably have a substituent, 5- or 6 It is a member, a monovalent heterocyclic group. Examples of the 5-membered monovalent heterocyclic group include a thienyl group, a frill group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isooxazolyl group, and a pyrrolidinyl group. Examples of the 6-membered monovalent heterocyclic group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridadinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, and a tetrahydropyranyl group.

R ^{1, R} 2, ^{R 3,} and R ^a heterocyclic group may monovalent optionally having a substituent represented by is more preferably, a thienyl group, a furyl group, a thiazolyl group, an oxazolyl group, pyridyl It is a group or a pyrazil group, and these groups may have a substituent.

R ^{1, R} 2, ^{R 3,} and monovalent substituent which may be a heterocyclic group optionally having represented by ^{R a} preferably, Cl -C 12 alkyl group (e.g., methyl group, trifluoromethyl Group, propyl group, hexyl group, octyl group, dodecyl group).

R ¹ and R ² are alkyl groups each independently which may have a substituent, and more preferably, an alkyl group having 1 to 15 carbon atoms which may have a substituent. Yes, more preferably an alkyl group having 1 to 12 carbon atoms, which may have a substituent, and even more preferably an alkyl group having 1 to 10 carbon atoms, which may have a substituent. It is a group, and more preferably, R ¹ and R ² are alkyl groups having 1 to 10 carbon atoms, which may have a substituent at the same time.

R ³ is 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, and further 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. Preferably, it is an alkyl group having 1 to 8 carbon atoms, which may have a substituent.

Here, the number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent.

^Ra is preferably a hydrogen atom.

R ^b is preferably an alkyl group which may have a substituent or an alkyloxy group which may have a substituent, and more preferably a carbon atom which may have a substituent. It is an alkyl group having the number 1 to 12, or an alkyloxy group having 1 to 12 carbon atoms, which may have a substituent, and more preferably, the number of carbon atoms, which may have a substituent. It is an alkyloxy group having 1 to 12 alkyl groups or an alkyloxy group having 1 to 6 carbon atoms, which may have a substituent, and more preferably a methyl group, an ethyl group, a 2-methylpropyl group or an octyl group. , Dodecyl group, or ethoxy group, and these groups may have a substituent. Here, the number of carbon atoms of the alkyl group and the alkyloxy group does not include the number of carbon atoms of the substituent.

R ^c is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and more preferably, the number of carbon atoms which may have a substituent. It is an alkyl group of 1 to 12 or an aryl group having 6 to 10 carbon atoms which may have a substituent, and more preferably, it may have a substituent and has 1 to 1 carbon atoms. It is an aryl group having 6 to 15 carbon atoms, which may have an alkyl group of 8 or a substituent, and more preferably a methyl group, an octyl group, a 2-methylpropyl group, or a phenyl group. , These groups may have substituents. Here, the number of carbon atoms of the alkyl group and the aryl group does not include the number of carbon atoms of the substituent.

Specific examples of the structural unit represented by the formula (1) include the structural units represented by the following formulas (1-1) to (1-24).

As the structural unit represented by the formula (1), the structural unit represented by the formulas (1-2) to (1-11) is preferable, and the structural units represented by the formulas (1-2) to (1-8) are represented. The structural unit to be formed is more preferable, and the structural unit represented by the formula (1-5) is further preferable.

Specific examples of the structural unit represented by the formula (2) include the structural units represented by the formulas (2-1) to (2-42).

As the structural unit represented by the formula (2), the structural unit represented by the formulas (2-1) to (2-30) is preferable, and the structural units represented by the formulas (2-2) to (2-7) are represented. The structural unit to be formed is more preferable, and the structural unit represented by the formula (2-3) is further preferable.

The polymer compound P preferably contains a unit in which the structural unit represented by the formula (1) and the structural unit represented by the formula (2) are directly bonded. Hereinafter, such a unit is also referred to as a unit (I-II).

The unit (I-II) is a unit in which the structural unit represented by the formula (1) and the structural unit represented by the formula (2) are directly combined without going through other structural units. be.
Examples of the unit (I-II) include units represented by the following formulas (I-II-1) to (I-II-4).

In formulas (I-II-1) to (I-II-4), X ¹ , X ² , Z, R ¹ , R ² , and R ³ have the same meanings as described above.

The polymer compound P may contain any structural unit other than the structural unit represented by the formula (1) and the structural unit represented by the formula (2). In a preferred embodiment, the polymer compound P comprises only the structural unit represented by the formula (1) and the structural unit represented by the formula (2).

The weight average molecular weight of the polymer compound P is preferably 1 × 10 ³ or more, more preferably 3 × 10 ³ , still more preferably 1 × 10 ⁴ or more, preferably 1 × ¹⁰⁸ or less, more preferably 1 ×. 10 ⁷ or less, more preferably 1 × 10 ⁶ or less. Here, the weight average molecular weight of the polymer compound P means a weight average molecular weight calculated by using gel permeation chromatography (GPC), using tetrahydrofuran as a mobile phase, and using a standard polystyrene sample.

[2. Method for producing polymer compound]
The method for producing the polymer compound P is not particularly limited, but a method using a Suzuki coupling reaction, a Stille coupling reaction, or the like is preferable from the viewpoint of easiness of synthesizing the polymer compound P.

As a method using the Suzuki coupling reaction, for example, the formula (100):
Q ^100- E ^1- Q ²⁰⁰ (100)
[In the formula, E ¹ represents a divalent group represented by the formula (1). Q ¹⁰⁰ and ^{Q 200} are the same or different and represent a boronic acid residue (-B _{(OH) 2)} or boric acid ester residue. ]
One or more compounds represented by and formula (200):
T ^1- E ^2- T ² (200)
[In the formula, E ² represents a divalent group represented by the formula (2). T ¹ and T ² are the same or different and represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an aryl alkyl sulfonate group. ]
Examples thereof include a production method having a step of reacting one or more kinds of compounds represented by (2) in the presence of a palladium catalyst and a base. Preferred examples of E ¹ include groups represented by the above formulas (1-1) to (1-24). Preferred examples of E ² include groups represented by the above formulas (2-1) to (2-42).

In this case, the total number of moles of one or more compounds represented by the formula (200) used in the reaction is excessive with respect to the total number of moles of one or more compounds represented by the formula (100). Is preferable. Assuming that the total number of moles of one or more compounds represented by the formula (200) used in the reaction is 1 mol, the total number of moles of one or more compounds represented by the formula (100) is 0.6 to 0. It is preferably 99 mol, more preferably 0.7 to 0.95 mol.

Examples of boric acid ester residues include groups represented by the following formulas.

In the formula, Me represents a methyl group and Et represents an ethyl group.

^{Examples of the halogen atom represented by T 1} and T ² in the formula (200) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of easiness of synthesizing the polymer compound P, it is preferably a bromine atom or an iodine atom, and more preferably a bromine atom.

^{Examples of the alkylsulfonate group represented by T 1} and T ² in the formula (200) include a methanesulfonate group, an ethanesulfonate group, and a trifluoromethanesulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the arylalkylsulfonate group include a benzylsulfonate group.

Specifically, examples of the method for carrying out the Suzuki coupling reaction include a method in which a palladium catalyst is used as a catalyst in an arbitrary solvent and the reaction is carried out in the presence of a base.

Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst, a Pd (II) catalyst and the like. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium and the like can be mentioned, but from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) speed. , Dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium are preferred.
The amount of the palladium catalyst added is not particularly limited and may be an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol with respect to 1 mol of the compound represented by the formula (100). It is preferably 0.0003 mol to 0.1 mol.

When palladium acetates are used as the palladium catalyst used in the Suzuki coupling reaction, for example, phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, and tri (o-methoxyphenyl) phosphine are added as ligands. can do. In this case, the amount of the ligand added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, and more preferably 1 mol to 10 mol with respect to 1 mol of the palladium catalyst. be.

Examples of the base used in the Suzuki coupling reaction include inorganic bases, organic bases, and inorganic salts. Examples of the inorganic base include potassium carbonate, sodium carbonate, barium hydroxide and the like. Examples of the organic base include triethylamine and tributylamine. Examples of the inorganic salt include cesium fluoride and the like.
The amount of the base added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, and more preferably 1 mol to 10 mol with respect to 1 mol of the compound represented by the formula (100). be.

The Suzuki coupling reaction is usually carried out in a solvent. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. From the viewpoint of solubility of the polymer compound P, toluene and tetrahydrofuran are preferable. Further, the base may be added as an aqueous solution and reacted in a two-phase system. When an inorganic salt is used as the base, it is usually added as an aqueous solution for reaction from the viewpoint of the solubility of the inorganic salt.
When the base is added as an aqueous solution and the reaction is carried out in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added, if necessary.

The temperature at which the Suzuki coupling reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and is preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound P. Alternatively, the temperature may be raised to near the boiling point of the solvent and reflux may be carried out. The reaction time may be set to the end point when the desired degree of polymerization is reached, but is usually about 0.1 hour to 200 hours. About 1 hour to 30 hours is efficient and preferable.

The Suzuki coupling reaction is carried out in a reaction system in which the Pd (0) catalyst is not inactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, the system is sufficiently degassed with argon gas, nitrogen gas, or the like. Specifically, after sufficiently substituting the inside of the polymerization vessel (reaction system) with nitrogen gas and degassing, the compound represented by the formula (100) and the compound represented by the formula (200) are placed in the polymerization vessel. Dichlorobis (triphenylphosphine) palladium (II) was charged, and the polymerization vessel was sufficiently replaced with nitrogen gas, degassed, and then bubbled with nitrogen gas in advance to add a degassed solvent such as toluene. After that, a base degassed by bubbling with nitrogen gas in advance, for example, an aqueous sodium carbonate solution is added dropwise to this solution, and then heated and heated, for example, while maintaining an inert atmosphere at a reflux temperature for 8 hours. Polymerize.

As a method using the Stille coupling reaction, for example, the formula (300):
Q ^300- E ^3- Q ⁴⁰⁰ (300)
[In the formula, E ³ represents a divalent group represented by the formula (1). Q ³⁰⁰ and ^{Q 400} are the same or different and represent an organotin residue. ]
One or more compounds represented by and the following formula (400):
T ^3- E ^4- T ⁴ (400)
[In the formula, E ⁴ represents a divalent group represented by the formula (2). T ³ and T ⁴ represent the same or different, halogen atom, alkyl sulfonate group, aryl sulfonate group or aryl alkyl sulfonate group. ]
Examples thereof include a production method having a step of reacting one or more kinds of compounds represented by (2) in the presence of a palladium catalyst. Preferred examples of E ³ include groups represented by the above formulas (1-1) to (1-24). Preferred examples of E ⁴ include groups represented by the above formulas (2-1) to (2-42).

Examples of the organotin residue include a group represented by ^{−SnR 100} _3. Here, R ¹⁰⁰ represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group and the like.
Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl gravel, n-pentyl group, isopentyl group, 2-methylbutyl. Group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, Examples thereof include a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl grave, an octadecyl group, and an icosyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. Examples of the aryl group include a phenyl group and a naphthyl group. Preferably -SnMe ₃ as organotin residue, -SnEt _3, -SnBu _3, an -SnPh _3, more preferably -SnMe _3, -SnEt _3, is -SnBu _3. In the above preferred example, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

^{Examples of the halogen atom represented by T 3} and T ⁴ in the formula (400) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of easiness of synthesizing the polymer compound P, it is preferably a bromine atom or an iodine atom.

In the formula (400), as the alkyl sulfonate group represented by T ³ and T ^4, methanesulfonate group, ethanesulfonate group, a trifluoromethane sulfonate group are exemplified. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the aryl sulfonate group include a benzyl sulfonate group.

Specifically, as the catalyst, for example, a method of reacting in an arbitrary solvent under a palladium catalyst can be mentioned.
Examples of the palladium catalyst used in the Stille coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specific examples thereof include palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, and bis (dibenzylideneacetone) palladium. From the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, palladium [tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferable.
The amount of the palladium catalyst added to the Stille coupling reaction is not particularly limited and may be an effective amount as a catalyst, but is usually 0.0001 with respect to 1 mol of the compound represented by the formula (400). It is from mol to 0.5 mol, preferably 0.0003 mol to 0.2 mol.

If necessary, a ligand or a co-catalyst can be used in the Stille coupling reaction. Examples of the ligand include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, and tris (2-furyl) phosphine, and triphenylarsine and triphenyloxyarsine. Examples include arsenic compounds. Examples of co-catalysts include copper iodide, copper bromide, copper chloride, copper 2-tenoylate (I) and the like.
When a ligand or co-catalyst is used, the amount of the ligand or co-catalyst added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, based on 1 mol of the palladium catalyst. , More preferably 1 mol to 10 mol.

The Stille coupling reaction is usually carried out in a solvent. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, dimethoxyethane, tetrahydrofuran and the like. From the viewpoint of solubility of the polymer compound P, toluene and tetrahydrofuran are preferable.

The temperature at which the Stille coupling reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and is preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound P. Alternatively, the temperature may be raised to near the boiling point of the solvent and reflux may be carried out.
The time for carrying out the reaction (reaction time) may be the end point when the desired degree of polymerization is reached, but is usually about 0.1 hour to 200 hours. About 1 hour to 30 hours is efficient and preferable.

The Stille coupling reaction is carried out in a reaction system in which the Pd catalyst is not inactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, the system is sufficiently degassed with argon gas, nitrogen gas, or the like. Specifically, after sufficiently substituting the inside of the polymerization vessel (reaction system) with nitrogen gas and degassing, the compound represented by the formula (300) and the compound represented by the formula (400) are placed in the polymerization vessel. A palladium catalyst is charged, the polymerization vessel is sufficiently replaced with nitrogen gas, degassed, and then bubbled with nitrogen gas in advance to add a degassed solvent, for example, toluene, and then coordinated as necessary. The compound and co-catalyst are added, and then the mixture is heated and heated, and polymerized at a reflux temperature for 6 to 8 hours while maintaining an inert atmosphere.

The compounds represented by the formulas (200) and (300) can be produced, for example, by the method described in International Publication No. 2011/05/2709.
The compound represented by the formula (400) can be produced, for example, by the method described in US Patent Application Publication No. 2013/0137848.
The compound represented by the formula (100) can be produced, for example, by the method described in US Patent Application Publication No. 2013/0137848 and the method described in International Publication No. 2011/052709.

[3. Compositions Containing Polymer Compounds]
The composition of the present embodiment contains the polymer compound P and an n-type semiconductor material. Examples of the polymer compound P contained in the composition of the present embodiment and preferred examples are described in [1. Polymer compound] as described above.

The n-type semiconductor material that can be contained in the composition may be a low molecular weight compound or a high molecular weight compound.

Examples of n-type semiconductor materials (electron-accepting compounds) that are low molecular weight compounds include oxadiazole derivatives, anthracinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, and tetracyano. anthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, fullerene and derivatives thereof such as C ₆₀ fullerene, and phenanthrene derivatives such as bathocuproine Can be mentioned.

Examples of n-type semiconductor materials (electron-accepting compounds) that are polymer compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives. Examples thereof include derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinolin and its derivatives, polyquinoxalin and its derivatives, and polyfluorene and its derivatives.

As the n-type semiconductor material, one or more selected from fullerenes and fullerene derivatives are preferable, and fullerene derivatives are more preferable.

Examples of fullerenes include C ₆₀ fullerenes, C ₇₀ fullerenes, C ₇₆ fullerenes, C ₇₈ fullerenes, and C ₈₄ fullerenes. Examples of fullerene derivatives include these fullerene derivatives. A fullerene derivative means a compound in which at least a part of fullerene is modified.

Examples of fullerene derivatives include compounds represented by the following formulas (N-1) to (N-4).

In equations (N-1) to (N-4),
^RX represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of ^RXs may be the same as or different from each other.
^RY represents an alkyl group or an aryl group. A plurality of ^RYs may be the same as or different from each other.

Examples of the monovalent heterocyclic group represented by R ^X is thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, quinolyl group, and isoquinolyl group.

Examples of groups having an ester structure represented by R ^X is a group represented by the formula (E1).

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

Examples of C ₆₀ fullerene derivatives include the following compounds.

Examples of C ₇₀ fullerene derivatives include the following compounds.

Specific examples of the fullerene derivative include [6,6] -phenyl-C61 butyrate methyl ester (C ₆₀ PCBM, [6, 6] -Phenyl C61 butyric acid methyl ester), [6,6] -phenyl-C71 methyl butyrate. Ester (C ₇₀ PCBM, [6,6] -Phenyl C71 butyric acid ester) _{, [6,6] -Phenyl-C85 butyrate methyl ester (C 84} PCBM, [6,6] -Phenyl C85 butyric acid ester) , And [6,6] -thienyl-C61 butyrate methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).

The weight ratio of the polymer compound P to the n-type semiconductor material (polymer compound P / n-type semiconductor material) in the composition is not particularly limited, but is preferably 1/100 or more, more preferably 10/100 or more. It is more preferably 20/100 or more, further preferably 40/100 or more, preferably 100/1 or less, more preferably 100/10 or less, still more preferably 100/20 or less, still more preferably 100/40 or less. ..

In addition to the polymer compound P and the n-type semiconductor material, the composition has a function of generating an electric charge by a surfactant, an ultraviolet absorber, an antioxidant, and absorbed light as long as the object and effect of the present invention are not impaired. It may contain any component such as a sensitizer for sensitizing and a light stabilizer for increasing the stability from ultraviolet rays.

The composition may be in the form of an ink comprising a solvent in addition to the polymeric compound P and the n-type semiconductor material. In the present specification, the ink may or may not be colored, and means a liquid composition used in the coating method. In the ink, the polymer compound P and the n-type semiconductor material, and any component may not be completely dissolved in the solvent, and the ink may be in the form of a dispersion liquid of these components. The ink will be described later.

[4. Photoelectric conversion element]
The polymer compound P may have absorption in the wavelength range of 1000 nm or more. Therefore, the photoelectric conversion element containing the polymer compound P in the active layer can convert light in the wavelength range of 1000 nm or more into an electric signal. Hereinafter, the photoelectric conversion element containing the polymer compound P will be described in detail.

The photoelectric conversion element containing the polymer compound P has one or more active layers containing the polymer compound P between a pair of electrodes whose at least one is transparent or translucent.
A preferred form of the photoelectric conversion element containing the polymer compound P is an active layer formed of a pair of electrodes whose at least one is transparent or translucent, and a composition containing a p-type semiconductor material and an n-type semiconductor material. Have. The polymer compound P is preferably used as a p-type organic semiconductor material. Therefore, the photoelectric conversion element according to the present embodiment preferably has an active layer containing the polymer compound P and the n-type semiconductor material. The p-type semiconductor material (electron-donating compound) and the n-type semiconductor material (electron-accepting compound) are relatively determined from the energy level of the energy level of these compounds.

Here, a configuration example that the photoelectric conversion element of the present embodiment can take will be described. FIG. 1 is a diagram schematically showing a configuration of a photoelectric conversion element of the present embodiment.

As shown in FIG. 1, the photoelectric conversion element 10 is provided on the support substrate 11. The photoelectric conversion element 10 is in contact with the first electrode 12 provided in contact with the support substrate 11, the electron transport layer 13 provided in contact with the first electrode 12, and the electron transport layer 13. The active layer 14 provided in the above, the hole transport layer 15 provided in contact with the active layer 14, and the second electrode 16 provided in contact with the hole transport layer 15 are provided. There is. In this configuration example, the sealing member 17 is further provided so as to be in contact with the second electrode 16. At the first electrode 12, electrons are sent to an external circuit. At the second electrode 16, electrons flow in from an external circuit.
Hereinafter, the components that can be included in the photoelectric conversion element of the present embodiment will be specifically described.

(substrate)
The photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed by a substrate (sealing substrate). Usually, one of a pair of electrodes is formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.

Examples of the substrate material include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the side opposite 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 translucent electrode. ..

(electrode)
The photoelectric conversion element includes a first electrode and a second electrode, which are a pair of electrodes. Of the pair of electrodes, at least one electrode is preferably a transparent or translucent electrode in order to allow light to enter.

Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, which are composites thereof, gold, platinum, silver, and the like. Copper is mentioned. As a transparent or translucent electrode material, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivative, polythiophene and its derivative as a material may be used. The transparent or translucent electrode may be the first electrode or the second electrode.

If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode having low light transmission. Examples of materials for electrodes having low light transmission include metals and conductive polymers. Specific examples of materials for electrodes with low light transmission include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, ytterbium, indium, cerium, samarium, and europium. Metals such as terbium and ytterbium, and two or more alloys of these, or one or more of these metals, and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin. Examples include alloys with one or more metals selected from the group consisting of, graphite, graphite interlayer compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

(Active layer)
The active layer contains the polymer compound P, and preferably further contains an n-type semiconductor material. The active layer may contain the polymer compound P alone or in any combination of two or more.
Examples of the polymer compound P that can be contained in the active layer and preferable examples are described in [1. It is the same as the example described in [Polymer compound] and the preferred example.
Examples of n-type semiconductor materials that can be contained in the active layer and preferable examples are described in [3. The same applies to the examples described in [Composition Containing Polymer Compounds] and the preferred examples.

(Middle class)
As shown in FIG. 1, the photoelectric conversion element of the present embodiment has, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, etc.) as a component for improving characteristics such as photoelectric conversion efficiency. It is preferable to have an intermediate layer (buffer layer) such as a hole injection layer).

Examples of materials used for 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 (poly (3,4-ethylenedioxythiophene)). 4-styrene sulfonate)) and a mixture (PEDOT: PSS) can be mentioned.

The intermediate layer can be formed by any conventionally known suitable forming method. The intermediate layer can be formed by a vacuum vapor deposition method, a coating method, or the like.

As shown in FIG. 1, the photoelectric conversion element preferably includes an electron transport layer as an intermediate layer between the first electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the first electrode.

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

The electron transport layer contains an electron transport material. Examples of electron-transporting materials include ethoxylated polyethyleneimine (PEIE), polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

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 preferable, and zinc oxide is particularly preferable.

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

As shown in FIG. 1, the photoelectric conversion element of the present embodiment preferably includes a hole transport layer as an intermediate layer between the second electrode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the second electrode. The hole transport layer may be in contact with the second electrode. The hole transport layer may be in contact with the active layer.

The hole transport layer provided in contact with the second electrode may be particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the second electrode has a function of promoting the injection of holes into the second electrode. The hole transport layer (hole injection layer) may be in contact with 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, tungsten oxide (WO ₃ ) and molybdenum oxide. (MoO ₃ ) can be mentioned.

In the photoelectric conversion element according to the present embodiment, the intermediate layers are an electron transport layer and a hole transport layer, and the substrate (support substrate), the first electrode, the electron transport layer, the active layer, the hole transport layer, and the second It is preferable to have a structure in which the electrodes of the above are laminated so as to be in contact with each other in this order.

(Sealing member)
It is preferable that the photoelectric conversion element of the present embodiment further includes a sealing member and is a sealed body sealed by such a sealing member.
Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate which is a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.

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

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

The sealing member is usually made of a material that can withstand the heat treatment performed when the photoelectric conversion element is applied, for example, when it is incorporated into the device of the following application example.

[5. Manufacturing method of photoelectric conversion element]
The method for manufacturing the photoelectric conversion element of the present embodiment is not particularly limited. The photoelectric conversion element of the present embodiment can be manufactured by combining a suitable forming method with a material selected for forming a component.

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

(Process to prepare the board)
In this step, for example, a support substrate provided with the first electrode is prepared. Further, a substrate provided with a conductive thin film formed of the electrode material described above is obtained from the market, and if necessary, the conductive thin film is patterned to form the first electrode. A support substrate provided with the first electrode can be prepared.

In the method for manufacturing a photoelectric conversion element according to the present embodiment, the method for forming the first electrode when forming the first electrode on the support substrate is not particularly limited. The first electrode has a structure in which the first electrode is formed by a conventionally known arbitrary suitable method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, a plating method, or a coating method from the material already described. Can be formed into.

(Formation process of electron transport layer)
The method for manufacturing a photoelectric conversion element may include a step of forming an electron transport layer (electron injection layer) provided between the active layer and the first electrode.

The method of forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the electron transport layer, it is preferable to form the electron transport layer by a conventionally known arbitrary suitable coating method. The electron transport layer can be formed by, for example, a coating method using a coating liquid containing the material and solvent of the electron transport layer, a vacuum deposition method, or the like, which has already been described.

(Process of forming active layer)
In the method for manufacturing a photoelectric conversion element of the present embodiment, an active layer is formed on the electron transport layer. The active layer, which is a main component, can be formed by any suitable conventionally known forming step. In the present embodiment, the active layer is preferably produced by a coating method using an ink (coating liquid).

Hereinafter, the steps (i) and (ii) included in the step of forming the active layer, which is a main component of the photoelectric conversion element of the present invention, and the ink that can be used in the step of forming the active layer will be described.

Step (i)
As a method of applying the ink to the application target, any suitable application method can be used. As the coating method, a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, an inkjet printing method, a nozzle coating method, or a capillary coating method is preferable. The die coating method, the slit coating method, the spin coating method, the capillary coating method, or the bar coating method is more preferable, and the slot die coating method, the slit coating method, or the spin coating method is further preferable.

(ink)
The ink for forming the active layer may be a solution, or may be a dispersion liquid such as a dispersion liquid, an emulsion (emulsion liquid), or a suspension (suspension). Hereinafter, the ink for forming the active layer will be described. An ink for forming a bulk heterojunction type active layer will be described as an example. Therefore, the ink for forming the active layer contains the polymer compound P as the p-type semiconductor material and the n-type semiconductor material, and further contains at least one type or two or more types of solvents.

The ink for forming the active layer may contain only one kind of each of the polymer compound P and the n-type semiconductor material, or may contain two or more kinds in any combination of two or more kinds.

Examples of the solvent that the ink can contain include an aromatic hydrocarbon solvent, a ketone solvent, an ester solvent, and a mixed solvent thereof. Specific examples of the aromatic hydrocarbon solvent include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene (psoidoctene)), Included are butylbenzene (eg, n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (eg, 1-methylnaphthalene), tetraline and indane.

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone.

Examples of ester solvents include ethyl acetate, butyl acetate, phenyl acetate, ethyl cellsolve acetate, methyl benzoate, butyl benzoate, and benzyl benzoate.

(Arbitrary ingredient)
In addition to the polymer compound P and n-type semiconductor materials, the ink has a function of generating electric charges by a surfactant, an ultraviolet absorber, an antioxidant, and absorbed light as long as the object and effect of the present invention are not impaired. It may contain any component such as a sensitizer for sensitizing and a light stabilizer for increasing the stability from ultraviolet rays.

(concentration)
The total concentration of the polymer compound P and the n-type semiconductor material in the ink is preferably 0.01% by weight or more and 20% by weight or less, and more preferably 0.01% by weight or more and 10% by weight or less. , 0.01% by weight or more and 5% by weight or less is more preferable, and 0.1% by weight or more and 5% by weight or less is particularly preferable. The polymer compound P and the n-type semiconductor material may be dissolved or dispersed in the ink. It is preferable that at least a part of the polymer compound P and the n-type semiconductor material is dissolved, and more preferably all of them are dissolved.

(Ink preparation)
The ink can be prepared by a known method. For example, a method of adding an n-type semiconductor material and a polymer compound P to a solvent, a method of adding a polymer compound P to a solvent, adding an n-type semiconductor material to another solvent, and then each solvent to which each material is added. Can be prepared by a method of mixing the above.

The solvent, the polymer compound P, and the p-type semiconductor material may be heated and mixed to a temperature equal to or lower than the boiling point of the solvent.

After mixing the solvent with the polymer compound P and the p-type semiconductor material, the obtained mixture may be filtered with a filter, and the obtained filtrate may be used as an ink. As the filter, for example, a filter formed of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.

The ink for forming the active layer is applied to a coating target selected according to the photoelectric conversion element and its manufacturing method. The ink for forming the active layer can be applied to the functional layer of the photoelectric conversion element in the manufacturing process of the photoelectric conversion element, and the functional layer in which the active layer can exist can be applied. Therefore, the target of applying the ink for forming the active layer differs depending on the layer structure and the order of layer formation of the photoelectric conversion element to be manufactured. For example, the photoelectric conversion element has a layer structure in which a substrate, a first electrode, an electron transport layer, an active layer, a hole transport layer, and a second electrode are laminated, and the layer described on the left side is When formed first, the target of application of the ink for forming the active layer is the electron transport layer. Further, for example, the photoelectric conversion element has a layer structure in which a substrate, a second electrode, a hole transport layer, an active layer, an electron transport layer, and a first electrode are laminated, and is described on the left side. When the layer is formed first, the target of application of the ink for forming the active layer is the hole transport layer.

Process (ii)
Any suitable method can be used as a method for removing the solvent from the coating film of the ink, that is, a method for removing the solvent from the coating film and solidifying it. Examples of the method for removing the solvent include a method of directly heating with a hot plate in an atmosphere of an inert gas such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a vacuum drying method. Such a drying method can be mentioned.

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

(Formation process of hole transport layer)
The method for manufacturing a photoelectric conversion element of the present embodiment includes a step of forming a hole transport layer (hole injection layer) provided on the active layer.

The method of forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by a conventionally known arbitrary suitable vacuum vapor deposition method.

(Forming process of the second electrode)
The method for forming the second electrode is not particularly limited. In the second electrode, for example, the material of the above-exemplified electrode is formed on the hole transport layer by any conventionally known suitable method such as a coating method, a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method. can do. The photoelectric conversion element of the present embodiment is manufactured by the above steps.

(Process of forming a sealed body)
In forming the encapsulant, in the present embodiment, a conventionally known arbitrary suitable encapsulant (adhesive) and substrate (encapsulating substrate) are used. Specifically, a sealing material such as a UV curable resin is applied onto the support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then bonded with the sealing material without gaps, and then UV. A encapsulated body of the photoelectric conversion element can be obtained by sealing the photoelectric conversion element in the gap between the support substrate and the sealing substrate by using a method suitable for the selected sealing material such as light irradiation. ..

(Application example of photoelectric conversion element)
The photoelectric conversion element according to the present embodiment is used as an optical detection element in a detection unit (sensor) provided in various electronic devices such as a workstation, a personal computer, a personal digital assistant, an entrance / exit management system, a digital camera, and a medical device. Can be applied.
In particular, the photoelectric conversion element according to the present embodiment can be applied to an image sensor and a biometric authentication device.

The photoelectric conversion element of the present embodiment includes, for example, an image detection unit (for example, an image sensor such as an X-ray sensor) for a solid-state image pickup device such as an X-ray image pickup device and a CMOS image sensor, and a fingerprint, which are included in the above-exemplified electronic device. Suitable for a detection unit (for example, a near infrared sensor) that detects a predetermined feature of a part of a living body such as a detection unit, a face detection unit, a vein detection unit, and an iris detection unit, and a detection unit of an optical biosensor such as a pulse oximeter. Can be applied to.

Hereinafter, among the detection units to which the photoelectric conversion element according to the present embodiment can be suitably applied, a configuration example of an image detection unit for a solid-state imaging device and a fingerprint detection unit for a biometric authentication device (for example, a fingerprint authentication device) will be described. , Will be described with reference to the drawings.

(Image detector)
FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state image sensor.

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

The CMOS transistor substrate 20 includes a conventionally known arbitrary suitable configuration in a mode according to the design.

The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.

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

A signal readout circuit and the like are built in the CMOS transistor substrate 20 by such functional elements and wiring.

The interlayer insulating film 30 can be made of any conventionally known suitable insulating material such as silicon oxide or an insulating resin. The interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

The sealing layer 40 can be made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. .. The sealing layer 40 can have the same structure as the sealing member 17 described above.

As the color filter 50, for example, a primary color filter that is made of a conventionally known arbitrary suitable material and that corresponds to the design of the image detection unit 1 can be used. Further, as the color filter 50, a complementary color filter that can be thinner than the primary color filter can also be used. Complementary color filters include, for example, three types (yellow, cyan, magenta), three types (yellow, cyan, transparent), three types (yellow, transparent, magenta), and three types (transparent, cyan, magenta). Color filters that combine types can be used. These can be arbitrarily arranged in a manner corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.

The light received by the photoelectric conversion element 10 via the color filter 50 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, an image pickup target. Is output as an electric signal corresponding to.

Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by a signal readout circuit built in the CMOS transistor substrate 20, which is not shown. Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.

(Fingerprint detector)
FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally configured with a display device.

The display device 2 of the mobile information terminal includes a fingerprint detection unit 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main component, and a display panel provided on the fingerprint detection unit 100 and displaying a predetermined image. It is provided with a unit 200.

In this configuration example, the fingerprint detection unit 100 is provided in an area that substantially coincides with the display area 200a of the display panel unit 200. In other words, the display panel unit 200 is integrally laminated above the fingerprint detection unit 100.

When fingerprint detection is performed only in a part of the display area 200a, the fingerprint detection unit 100 may be provided corresponding to only the part of the display area 200a.

The fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The fingerprint detection unit 100 desires any suitable conventionally known member such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown). It can be provided in a manner corresponding to the design so that the characteristics can be obtained. For the fingerprint detection unit 100, the configuration of the image detection unit already described can also be adopted.

The photoelectric conversion element 10 may be included in any aspect within the display region 200a. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (anode or cathode) in a matrix, for example.

The light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, the electricity corresponding to the captured fingerprint. It is output as a signal.

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

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

In the configuration example described above, the organic EL element 220 is used as a light source for pixels in the display area 200a and also as a light source for fingerprint imaging in the fingerprint detection unit 100.

Here, the operation of the fingerprint detection unit 100 will be briefly described.
When fingerprint authentication is executed, the fingerprint detection unit 100 detects a fingerprint using the light emitted from the organic EL element 220 of the display panel unit 200. Specifically, the light emitted from the organic EL element 220 passes through a component existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is displayed within the display area 200a. It is reflected by the skin (finger surface) of the fingertips of the fingers placed so as to be in contact with the surface of the panel portion 200. At least a part of the light reflected by the finger surface passes through the components existing between them and is received by the photoelectric conversion element 10, and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, image information about the fingerprint on the finger surface is constructed from the converted electric signal.

The portable information terminal provided with the display device 2 performs fingerprint authentication by comparing the obtained image information with the fingerprint data for fingerprint authentication recorded in advance by an arbitrary suitable step known conventionally.

Hereinafter, examples will be shown in order to explain the present invention in more detail. The present invention is not limited to the examples described below. Unless otherwise specified, the operations described below were performed under normal temperature and pressure conditions.

[Evaluation method]
(Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw))
The number average molecular weight and the weight average molecular weight of the compounds were determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp) as polystyrene-equivalent values. The measurement conditions are as follows.
Sample: A sample was prepared by dissolving the compound to be measured in tetrahydrofuran so as to have a concentration of about 0.5% by weight.
Injection volume: 30 μL
Mobile phase: tetrahydrofuran Flow velocity: 0.6 mL / min Column: A column in which two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series was used.
Detector: A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used.

[Synthesis of polymer compounds used in Examples and Comparative Examples]
In Examples and Comparative Examples, polymer compounds P-1 to P-3 having the following structural formulas were used.

Each polymer compound was synthesized according to the following.

(Synthesis of Polymer Compound P-1)

Compound 1 was prepared. Compound 1 can be produced by the method described in Example 53 of International Publication No. 2011/052709. Compound 2 was synthesized by the method described in US Patent Application Publication No. 2013/137884.

500 mg (0.475 mmol) of compound 1, 198 mg (0.425 mmol) of compound 2 and 32 mL of toluene were placed in a 200 mL flask in which the gas inside was replaced with nitrogen to prepare a uniform solution. The resulting toluene solution was bubbled with argon gas for 30 minutes. Then, 6.52 mg (0.007 mmol) of tris (dibenzylideneacetone) dipalladium and 13.0 mg (0.043 mmol) of tris (2-tolyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 6 hours. Then, 500 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 5 hours.

The flask was then cooled to 25 ° C. and the reaction was poured into 300 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was placed in a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of toluene, 2.0 g of sodium diethyldithiocarbamate and 40 mL of water were added, and the mixture was stirred under reflux for 8 hours.

After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and then 50 mL of 5% aqueous potassium fluoride solution. Washed twice with, then washed twice with 50 mL of water, and the resulting solution was poured into methanol to precipitate the polymer. The polymer was filtered and dried, the resulting polymer was redissolved in 50 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 160 mg of the polymer compound P-1. The molecular weight (in terms of polystyrene) of the polymer compound P-1 measured by GPC was 10,600 for Mn and 25,100 for Mw.

(Synthesis of Polymer Compound P-2)
The polymeric compound P-2 was synthesized according to the method described in paragraph [0381] (Example 54) of WO 2011/052709.

(Synthesis of Polymer Compound P-3)
The polymeric compound P-3 was synthesized according to the method described in paragraph [0401] (Example 64) of WO 2011/052709.

[Example 1]
(Manufacturing of ink containing solvent, manufacturing of photoelectric conversion element, evaluation of these)
(1) Manufacture of photoelectric conversion element and its encapsulant A glass substrate having an ITO film having a thickness of 50 nm was prepared by a sputtering method. The surface of the glass substrate was treated with ozone UV.

Next, as a buffer layer, ethoxylated polyethyleneimine (PEIE) (“polyethylenimine 80% ethoxylated solution (37 wt% aqueous solution)” manufactured by Sigma-Aldrich, product number: 306185) was applied onto the ITO film by spin coating. , The PEIE layer was prepared by heating in the air at 120 ° C. for 10 minutes.

Next, 1 part by weight of the polymer compound P-1 as the p-type semiconductor material and C60-PCBM (phenyl61-butyric acid methyl ester: manufactured by Frontier Carbon Co., Ltd., product name: nanom spectra) which is a fullerene derivative as the n-type semiconductor material. E100, hereinafter the same product is used for C60-PCBM) is mixed with 2 parts by weight and tetrahydronaphthalene as a solvent, and the mixture is heated and stirred at 60 ° C. for 8 hours to obtain high molecular weight compounds P-1, C60-PCBM. And tetrahydronaphthalene, an ink was produced. The total weight of the polymer compound P-1 and the weight of C60-PCBM was 4.5% by weight based on the weight of the ink.

The ink was applied onto the PEIE layer by spin coating to prepare an active layer containing the polymer compound P-1. The thickness of the active layer was about 200 nm.

Then, molybdenum oxide was deposited on the active layer with a vacuum vapor deposition machine to a thickness of 15 nm, and then silver was deposited to a thickness of 60 nm to prepare a photoelectric conversion element.

A UV curable sealant, which is a sealing material, was applied onto a glass substrate, which is a support substrate, so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate, which is a sealing substrate, was bonded. Then, by irradiating with UV light, the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate. As a result, a sealed body of the photoelectric conversion element was obtained. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm × 2 mm.

(2) Evaluation of photoelectric conversion element A reverse bias voltage of -2V is applied to the encapsulated body of the photoelectric conversion element manufactured, and the external quantum efficiency (EQE) at this applied voltage is measured by a solar simulator (CEP-2000, spectroscopy). It was measured and evaluated using (manufactured by Keiki Co., Ltd.). Specifically, with a reverse bias voltage of -2V applied to the encapsulant of the photoelectric conversion element, a constant number of photons (1.0 × 10 ¹⁶ ) is applied every 20 nm in the wavelength range of 300 nm to 1200 nm. The current value of the current generated when the light was irradiated was measured, and the EQE spectrum at a wavelength of 300 nm to 1200 nm was obtained by a known method. When the EQE values (%) at a wavelength of 1000 nm and a wavelength of 1100 nm were calculated, they were 20% and 13%, respectively. Since light having a wavelength of 1000 nm and a wavelength of 1100 nm can be photoelectrically converted, it is useful as a sensor for detecting light of the wavelength.

[Comparative Example 1]
The polymer compound P-2 was used instead of the polymer compound P-1. Except for the above items, a photoelectric conversion element and a sealed body thereof were manufactured and evaluated in the same manner as in Example 1. The EQE value (%) at a wavelength of 1100 nm was calculated to be 0%.

[Comparative Example 2]
The polymer compound P-3 was used instead of the polymer compound P-1. Except for the above items, a photoelectric conversion element and a sealed body thereof were manufactured and evaluated in the same manner as in Example 1. The EQE value (%) at a wavelength of 1100 nm was calculated to be 0%.

[result]
The evaluation results of Examples and Comparative Examples are shown in the table below.

[Discussion]
A photoelectric conversion element using the polymer compound P-2 or P-3 having a structural unit represented by the formula (1) but not having the structural unit represented by the formula (2) has a wavelength of 1000 nm and Each EQE value at a wavelength of 1100 nm is 0%, and light having a wavelength of 1000 nm or more is not photoelectrically converted.
Further, according to the EQE spectrum diagram described in FIG. 5 of Patent Document 1 (Japanese Unexamined Patent Publication No. 2015-172131), the EQE of the organic solar cell using the polymer 1 is 0% in the wavelength range of 1000 nm or more. You can see that it is close. Here, the polymer 1 does not have a structural unit represented by the formula (1).
Therefore, it can be seen that when the polymer compound does not have either the structural unit represented by the formula (1) or the structural unit represented by the formula (2), high EQE cannot be realized at a wavelength of 1000 nm or more. ..

1 Image detector 2 Display device 10 Photoelectric conversion element 11, 210 Support substrate 12 First electrode 13 Electron transport layer 14 Active layer 15 Hole transport layer 16 Second electrode 17 Sealing member 20 CMOS transistor substrate 30 Interlayer insulation film 32 Interlayer wiring part 40 Sealing layer 50 Color filter 100 Fingerprint detection part 200 Display panel part 200a Display area 220 Organic EL element 230 Touch sensor panel 240 Sealing substrate

Claims (12)

A polymer compound containing a structural unit represented by the formula (1) and a structural unit represented by the formula (2).

(During the ceremony,
X ¹ and X ² independently represent a sulfur atom or an oxygen atom, respectively.
Z represents a nitrogen atom or a group represented by ^{−C (Ra) =.
R 1, R 2, R 3} , and ^{R a} are each independently,
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
Cycloalkynyl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Aryl groups that may have substituents,
Aryloxy groups, which may have substituents,
Arylthio groups, which may have substituents,
A monovalent heterocyclic group which may have a substituent,
Represents a group represented by -C (= O) -R ^b or a group represented by -SO _2- R ^c .
R ^b and R ^c are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Aryl groups that may have substituents,
Alkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent. ) The polymer compound according to claim 1, wherein the structural unit represented by the formula (1) and the structural unit represented by the formula (2) are directly bonded to each other. The polymer compound according to claim 1 or 2, wherein the structural unit comprises only the structural unit represented by the formula (1) and the structural unit represented by the formula (2). The polymer compound according to any one of claims 1 to 3, wherein Z is a nitrogen atom. The polymer compound according to any one of claims 1 to 4, wherein X ¹ and X ^{2 are sulfur atoms, respectively.} The polymer compound according to any one of claims 1 to 5, wherein R ¹ , R ² , and R ^{3 are alkyl groups that may independently have a substituent.} A composition comprising the polymer compound according to any one of claims 1 to 6 and an n-type semiconductor material. An ink containing the polymer compound according to any one of claims 1 to 6, an n-type semiconductor material, and a solvent. A photoelectric conversion element containing the polymer compound according to any one of claims 1 to 6. The photoelectric conversion element according to claim 9, which is an optical detection element. An image sensor comprising the photoelectric conversion element according to claim 9 or 10. A biometric authentication device comprising the photoelectric conversion element according to claim 9 or 10.

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