WO2014021109A1

WO2014021109A1 - Polymer compound, and organic semiconductor element and organic transistor which use said polymer compound

Info

Publication number: WO2014021109A1
Application number: PCT/JP2013/069439
Authority: WO
Inventors: 友也樫木; 和男瀧宮; 格尾坂
Original assignee: 住友化学株式会社; 国立大学法人広島大学
Priority date: 2012-08-03
Filing date: 2013-07-17
Publication date: 2014-02-06
Also published as: JP2014031446A; JP5914238B2

Abstract

Provided is a polymer compound capable of exhibiting excellent electron field effect mobility when used as a constituent material of an active layer of an organic transistor. The polymer compound includes structural units represented by formula (1) (in formula (1): ring A and ring B each independently represent an aromatic hydrocarbon ring or a heterocyclic ring; and R1 represents hydrogen, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen, an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group, or a cyano group, and these groups may have substituent groups).

Description

Polymer compound, and organic semiconductor device and organic transistor using the polymer compound

The present invention relates to a polymer compound, and an organic semiconductor element and an organic transistor using the polymer compound.

Compared with conventional transistors using inorganic semiconductor materials, organic transistors using organic semiconductor materials can be expected to reduce the weight of the device and reduce manufacturing costs. Because it is expected that it can be manufactured without any problems, research and development is actively conducted.

The field effect mobility, which is one of the indexes related to the performance of the organic transistor, greatly depends on the field effect mobility of the organic semiconductor material contained in the active layer. Therefore, various organic semiconductor materials have been studied in order to realize an organic transistor having excellent field effect mobility.

For example, according to Non-Patent Document 1, a compound having the following structure has been proposed.

However, the organic transistor including the compound according to Non-Patent Document 1 in the active layer does not have sufficient field effect mobility.

This invention is made | formed in view of such a situation, and when using as a constituent material of the active layer of an organic transistor, providing the high molecular compound which can exhibit the outstanding field effect mobility. Objective.

Another object of the present invention is to provide an organic semiconductor element and an organic transistor using the polymer compound.

The present invention provides the following polymer compounds [1] to [8], organic semiconductor elements and organic transistors.

[1] A polymer compound comprising a structural unit represented by the following formula (1).

(In the formula (1),
A ring and B ring each independently represent an aromatic hydrocarbon ring or a heterocyclic ring.
R ¹ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group Represents an acyloxy group, an amide group, a carboxy group, a nitro group or a cyano group, and these groups optionally have a substituent. Two R ¹ may be different from each other. )
[2] The polymer compound according to [1], wherein the A ring and the B ring are both the same aromatic hydrocarbon ring or heterocyclic ring.
[3] The polymer compound according to [1], wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (2).

(In the formula (2),
R ¹ represents the same meaning as described above.
X represents a group represented by ═CR ² — and a group represented by ═N—. A plurality of Xs may be different from each other. R ² is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group Represents an acyloxy group, an amide group, a carboxy group, a nitro group or a cyano group, and these groups optionally have a substituent. )
[4] The polymer compound according to [3], wherein a plurality of the Xs are all groups represented by ═CR ² —.
[5] The polymer compound according to any one of [1] to [4], further having a structural unit represented by the following formula (3).

(In formula (3),
Y represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. )
[6] An organic semiconductor material comprising the polymer compound according to any one of [1] to [5].
[7] An organic semiconductor element having an organic layer containing the organic semiconductor material according to [6].
[8] An organic transistor having a source electrode, a drain electrode, a gate electrode, and an active layer, wherein the active layer includes the organic semiconductor material according to [6].

Since the organic transistor containing the polymer compound of the present invention in the active layer has high field effect mobility, the present invention is extremely useful.

FIG. 1 is a schematic cross-sectional view showing a configuration example (1) of an organic transistor of the present invention. FIG. 2 is a schematic cross-sectional view showing a configuration example (2) of the organic transistor of the present invention. FIG. 3 is a schematic cross-sectional view showing a configuration example (3) of the organic transistor of the present invention. FIG. 4 is a schematic cross-sectional view showing a configuration example (4) of the organic transistor of the present invention. FIG. 5 is a schematic cross-sectional view showing a structural example (5) of the organic transistor of the present invention. FIG. 6 is a schematic cross-sectional view showing a configuration example (6) of the organic transistor of the present invention. FIG. 7: is typical sectional drawing which shows the structural example (7) of the organic transistor of this invention. FIG. 8: is typical sectional drawing which shows the structural example (8) of the organic transistor of this invention. FIG. 9 is a schematic cross-sectional view showing a structural example (9) of the organic transistor of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the description of the drawings, the same components are denoted by the same reference numerals, and redundant descriptions may be omitted.

In the present specification, the “structural unit” means a unit structure existing in one or more polymer compounds. The “structural unit” is preferably contained in the polymer compound as a “repeating unit” (that is, a unit structure present in two or more in the polymer compound).

In the present specification, “optionally substituted” means that all hydrogen atoms constituting the compound or group are unsubstituted, and that one or more hydrogen atoms are partially or completely substituted. Includes both embodiments when substituted by a group.
Examples of substituents include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, monovalent heterocyclic groups, aryloxy groups, arylthio groups, alkenyl groups, alkynyl groups, amino groups, silyl groups, halogen atoms, and acyl groups. , Acyloxy group, amide group, carboxy group, nitro group and cyano group. Among these substituents, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, a halogen atom or a cyano group are preferable, and an alkyl group, an alkoxy group, an aryl group, A monovalent heterocyclic group, aryloxy group or halogen atom is more preferred, and an alkyl group, alkoxy group or halogen atom is still more preferred. The alkyl group, alkoxy group, and alkylthio group may each be linear, branched, or cyclic.

<Polymer compound>
(First structural unit)
The polymer compound of the present invention includes a structural unit represented by the following formula (1), that is, a first structural unit.

The first structural unit represented by the above formula (1) may be contained in the polymer compound alone or in a combination of two or more.

In formula (1), A ring and B ring each independently represent an aromatic hydrocarbon ring or a heterocyclic ring.

The number of carbon atoms in the aromatic hydrocarbon ring is preferably 5 to 30, more preferably 6 to 14, and further preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, and a fluorene ring.

The number of carbon atoms in the heterocyclic ring is preferably 2 to 60, more preferably 2 to 22, and further preferably 3 to 14. The number of carbon atoms does not include the number of carbon atoms of the substituent. Specific examples of the heterocyclic ring include thiazole ring, thiophene ring, pyrrole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, benzothiophene ring, benzopyrrole ring, benzofuran ring, quinoline ring, isoquinoline ring, thienothiophene ring, Examples thereof include a benzothiadiazole ring.

In the formula (1), the A ring and the B ring are preferably the same aromatic hydrocarbon ring or heterocyclic ring from the viewpoint of easy synthesis of the polymer compound of the present invention, and are the same as each other. It is more preferably an aromatic hydrocarbon ring which is a 5-membered ring or a 6-membered ring or a heterocyclic ring which is the same 5-membered ring or 6-membered ring.

In formula (1), each R ¹ independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, amino Represents a group, a silyl group, a halogen atom, an acyl group, an acyloxy group, an amide group, a carboxy group, a nitro group or a cyano group, which may have a substituent, and two R ^{1 s} are different from each other. May be.

The alkyl group represented by R ¹ may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms of the linear alkyl group is usually 1 to 60, preferably 1 to 20, excluding the number of carbon atoms of the substituent. The number of carbon atoms of the branched alkyl group and the cyclic alkyl group is usually 3 to 20, preferably 4 to 20, not including the carbon atom number of the substituent. Among these alkyl groups, a linear alkyl group and a branched alkyl group are preferable, and a linear alkyl group is more preferable.

Examples of the alkyl group represented by R ¹ include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, a hexadecyl group; an isopropyl group, an isobutyl group, Examples thereof include branched alkyl groups such as sec-butyl group, tert-butyl group, 2-ethylhexyl group and 3,7-dimethyloctyl group; and cyclic alkyl groups such as cyclopentyl group and cyclohexyl group.

Examples of the substituent that the alkyl group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

The alkoxy group represented by R ¹ may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms of the linear alkoxy group is usually 1 to 20 without including the number of carbon atoms of the substituent. The number of carbon atoms of the branched alkoxy group and the cyclic alkoxy group is usually 3 to 20, excluding the number of carbon atoms of the substituent. Among these alkoxy groups, a linear alkoxy group is preferable.

Specific examples of the alkoxy group represented by R ¹ include a butyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, a 3,7-dimethyloctyloxy group, a dodecyloxy group, a hexadecyloxy group, and the like. A straight-chain alkoxy group such as hexyloxy group, dodecyloxy group, hexadecyloxy and the like is preferable.
Examples of the substituent that the alkoxy group may have include an aryl group and a halogen atom.

The alkylthio group represented by R ¹ may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms of the linear alkylthio group is usually 1 to 20, not including the number of carbon atoms of the substituent. The number of carbon atoms of the branched alkylthio group and the cyclic alkylthio group is usually 3 to 20, excluding the number of carbon atoms of the substituent. Among these alkylthio groups, a linear alkylthio group is preferable.

Specific examples of the alkylthio group represented by R ¹ include a butylthio group, a hexylthio group, a 2-ethylhexylthio group, a 3,7-dimethyloctylthio group, a dodecylthio group, a hexadecylthio group, a butylthio group, a hexylthio group, A linear alkylthio group such as dodecylthio group or hexadecylthio group is preferred.
Examples of the substituent that the alkylthio group may have include an aryl group and a halogen atom.

The aryl group represented by R ¹ is a remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom directly bonded to a ring from an aromatic hydrocarbon which may have a substituent, and benzene A group having two or more rings selected from a group having a ring, a group having a condensed ring, an independent aromatic hydrocarbon ring and a condensed ring is also included. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 20, excluding the number of carbon atoms of the substituent.

Specific examples of the aryl group represented by R ¹ include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyrenyl group. Group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 4-phenylphenyl group and the like.

Examples of the substituent that the aryl group represented by R ¹ may have include an alkyl group, an alkoxy group, an alkylthio group, a monovalent heterocyclic group, and a halogen atom. Among these, an alkyl group is preferable. . Specific examples of the aryl group having a substituent include a 4-hexylphenyl group, a 3,5-dimethoxyphenyl group, and a pentafluorophenyl group.

The monovalent heterocyclic group represented by R ¹ is 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. And a group in which two or more rings selected from a group having a condensed ring, an independent heterocyclic ring and a condensed ring are directly bonded. As the monovalent heterocyclic group, an aromatic heterocyclic group is preferable. The number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 3 to 20, excluding the number of carbon atoms of the substituent. Here, the heterocyclic compound is an organic compound having a ring structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. A compound containing a heteroatom.

Specific examples of the monovalent heterocyclic group represented by R ¹ include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2- Examples include oxazolyl group, 2-thiazolyl group, 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group and the like.

Examples of the substituent that the monovalent heterocyclic group represented by R ¹ may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and a halogen atom. Among these, an alkyl group Is preferred. Specific examples of the monovalent heterocyclic group having a substituent include 5-octyl-2-thienyl group and 5-phenyl-2-furyl group.

The aryloxy group represented by R ¹ may have a substituent. The number of carbon atoms of the aryloxy group is usually 6 to 20 without including the number of carbon atoms of the substituent.
Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.
Examples of the substituent that the aryloxy group represented by R ¹ may have include an alkyl group, an alkoxy group, and a halogen atom, and among these, an alkyl group is preferable.

The arylthio group represented by R ¹ may have a substituent. The number of carbon atoms of the arylthio group is usually 6 to 20, excluding the number of carbon atoms of the substituent.
Specific examples of the arylthio group represented by R ¹ include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and the like.
Examples of the substituent that the arylthio group represented by R ¹ may have include an alkyl group, an alkoxy group, and a halogen atom, and among these, an alkyl group is preferable.

The alkenyl group represented by R ¹ may have a substituent. The number of carbon atoms of the alkenyl group is usually 2 to 20, not including the number of carbon atoms of the substituent.
Specific examples of the alkenyl group represented by R ¹ include a vinyl group and a 1-octenyl group.
Examples of the substituent that the alkenyl group represented by R ¹ may have include an alkyl group, an alkoxy group, and a halogen atom.

The alkynyl group represented by R ¹ may have a substituent. The number of carbon atoms of the alkynyl group represented by R ¹ is usually 2 to 20 without including the number of carbon atoms of the substituent.
Specific examples of the alkynyl group represented by R ¹ include ethynyl group and 1-octynyl group.
Examples of the substituent that the alkynyl group represented by R ¹ may have include an alkyl group, an aryl group, and a silyl group. Specific examples of the alkynyl group having a substituent include 2-phenylethynyl group and trimethylsilylethynyl group.

The amino group represented by R ¹ may have a substituent. Examples of the substituent that the amino group represented by R ¹ may have include an alkyl group, an aryl group, and a monovalent heterocyclic group. Specific examples of the amino group having a substituent include a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a dicyclohexylamino group, a pyrrolidyl group, a piperidyl group, a phenylamino group, a diphenylamino group, and a 1-naphthylamino group. 2-naphthylamino group, pyridylamino group, and the like.

The silyl group represented by R ¹ may have a substituent. Examples of the substituent that the silyl group represented by R ¹ may have include an alkyl group, an aryl group, and an alkoxy group. Specific examples of the silyl group having a substituent include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group. And dimethylphenylsilyl group.

Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The acyl group represented by R ¹ may have a substituent. The number of carbon atoms of the acyl group represented by R ¹ is usually 1 to 20 without including the number of carbon atoms of the substituent. Specific examples of the acyl group represented by R ¹ include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the substituent that the acyl group represented by R ¹ may have include an alkyl group, an aryl group, and a halogen atom. Specific examples of the acyl group having a substituent include a trifluoroacetyl group and a pentafluorobenzoyl group.

The acyloxy group represented by R ¹ may have a substituent. The number of carbon atoms of the acyloxy group represented by R ¹ is usually 2 to 20, excluding the number of carbon atoms of the substituent. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, and a benzoyloxy group.
Examples of the acyloxy group that the acyloxy group represented by R ¹ may have include an alkyl group, an aryl group, and a halogen atom. Specific examples of the acyloxy group having a substituent include a trifluoroacetyloxy group and a pentafluorobenzoyloxy group.

The amide group represented by R ¹ may have a substituent. Specific examples of the amide group which may have a substituent include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, And dibenzamide group.

R ¹ is a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an alkenyl group, an alkynyl group, an acyl group, an acyloxy group, a cyano group, or a silyl group from the viewpoint of ease of synthesis of the compound of the present invention. Are preferable, a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a cyano group, and a silyl group are more preferable, and an aryl group, a monovalent heterocyclic group, and a silyl group are more preferable.

The first structural unit represented by the above formula (1) is preferably a structural unit represented by the following formula (2) from the viewpoint of ease of synthesis of the compound of the present invention.

In formula (2),
R ¹ represents the same meaning as described above.
X represents a group represented by ═CR ² — and a group represented by ═N—. A plurality of Xs may be different from each other. R ² is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group Represents an acyloxy group, an amide group, a carboxy group, a nitro group or a cyano group, and these groups optionally have a substituent.

In formula (2), an alkyl group represented by R ² , an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, Definition of halogen atom, acyl group, acyloxy group, amide group, carboxy group, specific examples are alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group represented by R ^1. , Arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, amide group, carboxy group, the same as the specific examples.

In formula (2), X represents a group represented by ═CR ² — and a group represented by ═N—. A plurality of Xs may be different from each other.

A plurality of Xs are preferably groups in which 4 to 6 of them are a group represented by ═CR ² — from the viewpoint of ease of synthesis of a monomer that is a raw material of the polymer compound of the present invention. More preferably, all six are groups represented by ═CR ² —.

R ² is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, from the viewpoint of obtaining higher field effect mobility and the ease of synthesis of the monomer that is a raw material for the polymer compound of the present invention. An atom and a cyano group are preferable, and a hydrogen atom, an alkyl group, and a halogen atom are more preferable.

Examples of the first structural unit include structural units represented by the following formula (1-1) to the following formula (1-19).

In the formulas (1-1) to (1-19), R ¹ and R ² are as defined above. R ^N are each independently a hydrogen atom, an alkyl group, an aryl group, monovalent heterocyclic group or an acyl group. Alkyl group, an aryl group represented by R ^N, 1-valent heterocyclic group or an acyl group may have a substituent. Alkyl group represented by R ^N, an aryl group, a monovalent heterocyclic group, the definition of the acyl group, specific examples include alkyl groups represented by the aforementioned R ^1, aryl group, monovalent heterocyclic group, acyl The definition of the group and the specific example are the same.

Among the structural units represented by the formulas (1-1) to (1-19), from the viewpoint of ease of synthesis of the monomer that is a raw material of the polymer compound of the present invention, the formula (1-1) Formula (1-2), Formula (1-8), Formula (1-10), Formula (1-15), Formula (1-16), and Formula (1-18) are preferable, and Formula (1-1) ), Structural units represented by formula (1-8), formula (1-10), and formula (1-18) are more preferred.

(Second structural unit)
The second structural unit is at least one structural unit selected from the group consisting of structural units represented by the following formula (3). Only one type of the second structural unit may be contained in the polymer compound, or two or more types of the second structural unit may be contained.

In formula (3), Y represents an arylene group or a divalent heterocyclic group, and these groups may have a substituent.

The arylene group represented by Y is an atomic group obtained by removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon which may have a substituent, A group in which two or more selected from a group having, a group having a condensed ring, an independent benzene ring and a condensed ring are directly bonded. The number of carbon atoms contained in the arylene group represented by Y (not including the carbon atoms of the substituents described later) is usually 6 to 60, and preferably 6 to 20.

Examples of the substituent of the arylene group represented by Y include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, and an amino group. Silyl group, halogen atom, acyl group, acyloxy group, amide group, carboxy group, nitro group or cyano group. Alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, amide group, definition of a carboxy group, specific examples, the alkyl group represented by R ^1, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, Definitions and specific examples of silyl group, halogen atom, acyl group, acyloxy group, amide group and carboxy group are the same.

Specific examples of the arylene group represented by Y include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a tetracenediyl group, a pyrenediyl group, a pentacenediyl group, a perylenediyl group, and a fluorenediyl group.

The arylene group represented by Y is preferably a group represented by the following formula (9-1) to the following formula (9-6), represented by the formula (9-1) or the formula (9-6). Groups are more preferred.

In the formulas (9-1) to (9-6), R represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group. Represents an amino group, a silyl group, a halogen atom, an acyl group, an acyloxy group, an amide group, a carboxy group, a nitro group or a cyano group, and these groups may have a substituent.

Alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy represented by R Group, amide group, carboxy group, nitro group or cyano group. Alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, amide group, definition of a carboxy group, specific examples, the alkyl group represented by R ^1, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, Definitions and specific examples of silyl group, halogen atom, acyl group, acyloxy group, amide group and carboxy group are the same.

The divalent heterocyclic group represented by Y is a remaining atomic group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the heterocyclic compound which may have a substituent. , A group having a condensed ring, a group in which two or more selected from an independent heterocyclic ring and a condensed ring are directly bonded. The number of carbon atoms possessed by the divalent heterocyclic group does not include the number of carbon atoms of the substituent, and is usually from 2 to 60, and preferably from 3 to 20.

Examples of the substituent that the divalent heterocyclic group represented by Y has include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, and an alkynyl. Group, amino group, silyl group, halogen atom, acyl group, acyloxy group, amide group, carboxy group, nitro group or cyano group. Alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, amide group Definitions and specific examples include an alkyl group represented by R ¹ , an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, The definition and specific examples of the halogen atom, acyl group, acyloxy group and amide group are the same.

Specific examples of the divalent heterocyclic group represented by Y include oxadiazole diyl group, thiadiazole diyl group, oxazole diyl group, thiazole diyl group, thiophene diyl group, bithiophene diyl group, terthiophene diyl group, quater Terthiophene diyl group, pyrrole diyl group, frangiyl group, selenophene diyl group, pyridine diyl group, pyrazine diyl group, pyrimidine diyl group, triazine diyl group, benzothiophene diyl group, benzopyrrole diyl group, benzofuran diyl group, quinoline diyl group, isoquinoline Examples thereof include a diyl group, a thienothiophene diyl group, a benzodithiophene diyl group, a benzothiadiazole diyl group, and a quinoxaline diyl group.

Examples of the divalent heterocyclic group represented by Y include groups represented by formula (10-1) to formula (10-26). Among these, since higher field effect mobility can be obtained, the structural units represented by the formulas (10-1) to (10-20) are preferable, and the formulas (10-1) and (10-3) are preferable. And structural units represented by formulas (10-6), (10-7), formula (10-11), formula (10-15), formula (10-17), and formula (10-20) are more preferable. Further preferred are structural units represented by formula (10-1), formula (10-15), formula (10-17) and formula (10-20).

In the formulas (10-1) to (10-26), R is as defined above.

Y is a bond between carbon atoms or a bond between a carbon atom and a hetero atom in a skeleton that is a main chain of the polymer compound when forming a polymer compound together with the structural unit represented by the formula (1). Thus, the group is preferably selected so that a π-conjugated system in which multiple bonds and single bonds are alternately repeated is formed. Examples of such a π-conjugated structure include a structure surrounded by a broken line in the following formula (E1).

The polymer compound of the present invention preferably has a structural unit in which two or more second structural units which may be different from each other are continuously bonded. Examples of the polymer compound including a structural unit in which two or more second structural units are continuously bonded include a polymer including a structural unit represented by the following formula (4-1) to the following formula (4-9) Compounds. Among these, from the viewpoint of improving the field effect mobility of the polymer compound, it is represented by Formula (4-1), Formula (4-5), Formula (4-7), and Formula (4-9). A polymer compound containing a structural unit is preferred.

In formulas (4-1) to (4-9), R represents the same meaning as described above.

(Other structural units)
The polymer compound of the present invention may contain a structural unit other than the first structural unit and the second structural unit (hereinafter sometimes referred to as “other structural unit”). Other structural units may be included in the polymer compound alone or in combination of two or more.

Examples of the other structural unit include an arylene group, a divalent heterocyclic group, a group represented by —CR ^c ═CR ^d —, a group represented by —C≡C—, and a group represented by —CR ^g ₂ —. A group represented by —C (═O) — and a group represented by —C (═O) O—.

The definitions and specific examples of the arylene group and divalent heterocyclic ring are the same as the definitions and specific examples of the arylene group and divalent heterocyclic group represented by Y above.

In the group represented by —CR ^c ═CR ^d — and the group represented by —CR ^g ₂ —, R ^c , R ^d and R ^g are each independently a hydrogen atom, an alkyl group, an aryl group, It represents a monovalent heterocyclic group, a halogen atom or a cyano group, and these groups optionally have a substituent.
Examples of the substituent that R ^c , R ^d and R ^g may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, a halogen atom, and the like. Of these, an alkyl group is preferred.

(Polymer compound)
The polymer compound of the present invention is preferably a conjugated polymer compound because more excellent field effect mobility can be obtained.

Since the polymer compound of the present invention has a better field effect mobility, the total molar ratio of the first structural unit and the second structural unit is 50 with respect to all the structural units constituting the polymer compound. It is preferably at least mol%, more preferably at least 70 mol%.

In the polymer compound of the present invention, if a polymerization reactive group remains at the molecular chain terminal, the field effect mobility may be lowered. Therefore, the molecular chain terminal is preferably a stable group such as an aryl group or a monovalent heterocyclic group.

The polymer compound of the present invention may be any type of copolymer, such as a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer.

The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound of the present invention is usually from 1 × 10 ³ to 1 × 10 ^8. The converted weight average molecular weight (Mw) is usually 1 × 10 ³ to 2 × 10 ⁸ . From the viewpoint of forming a thin film with good film quality, the number average molecular weight of the polymer compound is preferably 1 × 10 ³ or more, and the weight average molecular weight of the polymer compound is preferably 1 × 10 ³ or more. From the viewpoint of solubility and film formability, the polymer compound preferably has a number average molecular weight of 1 × 10 ⁶ or less, and the polymer compound preferably has a weight average molecular weight of 1 × 10 ⁶ or less.

<Method for producing polymer compound>
Next, a method for producing the polymer compound of the present invention will be described.
The polymer compound of the present invention may be produced by any method. As the polymer compound, for example, a compound represented by the formula: X ¹¹ -A ¹¹ -X ¹² and a compound represented by the formula: X ¹³ -A ¹² -X ¹⁴ are dissolved in an organic solvent as necessary. In addition, it can be produced by a known polymerization method such as aryl coupling using a suitable catalyst by adding a base as necessary.

In the above formula, A ¹¹ is a structural unit represented by the formula (1), and A ¹² is a structural unit represented by the formula (3).

In the above formula, X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a polymerization reactive group.

Examples of the polymerization reactive group include a halogen atom, a boric acid ester residue, a boric acid residue (such as a group represented by —B (OH) ₂ ), a trialkylstannyl group, and the like.

Examples of the halogen atom that is the polymerization reactive group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the boric acid ester residue that is the polymerization reactive group include a group represented by the following formula.

Examples of the trialkylstannyl group that is the polymerization reactive group include a trimethylstannyl group and a tributylstannyl group.

Examples of the polymerization method such as aryl coupling include polymerization by Suzuki coupling reaction (Chemical Review, 1995, 95, 2457-2483), polymerization by Stille coupling reaction (European Polymer Journal). 2005, 41, 2923-2933).

The polymerization reactive group is a halogen atom, a boric acid ester residue, a boric acid residue or the like when a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction is used. From the viewpoint of simplicity of the polymerization reaction, a bromine atom, an iodine atom, and a boric acid ester residue are preferable.
When the polymer compound of the present invention is polymerized by Suzuki coupling reaction, the ratio of the total mole number of bromine atom and iodine atom and the total mole number of boric acid ester residue, which are the above-mentioned polymerization reactive groups, is 0.00. It is preferably 7 to 1.3, and more preferably 0.8 to 1.2.

The polymerization reactive group is a halogen atom, a trialkylstannyl group or the like when a palladium catalyst such as Stille coupling reaction is used. From the viewpoint of simplicity of the polymerization reaction, the polymerization reactive group is preferably a bromine atom, an iodine atom, or a trialkylstannyl group.
When the polymer compound of the present invention is polymerized by a Stille coupling reaction, the ratio of the total mole number of bromine atom and iodine atom and the total mole number of trialkylstannyl group, which are the above-mentioned polymerization reactive groups, is 0.00. It is preferably 7 to 1.3, and more preferably 0.8 to 1.2.

Examples of the organic solvent used in the polymerization method include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane and the like. These organic solvents may be used alone or in combination of two or more.

Examples of the base used in the polymerization method include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, odor And organic bases such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.

The catalyst used in the polymerization method is a transition metal complex such as tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, dichlorobistriphenylphosphine palladium and the like, if necessary, It is a catalyst comprising a ligand such as triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine. These catalysts may be synthesized and used in advance, or the catalyst prepared in the reaction system may be used as it is. Moreover, these catalysts may be used individually by 1 type, or may use 2 or more types together.

The reaction temperature in the polymerization method is preferably 0 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C., and further preferably 0 ° C. to 120 ° C.

The reaction time in the polymerization method is usually 1 hour or more, preferably 2 to 500 hours.

The post-treatment of the polymerization reaction can be performed by a known method, for example, by a method of adding a reaction liquid obtained by the polymerization to a lower alcohol such as methanol and filtering and drying the deposited precipitate. it can.

When the purity of the polymer compound of the present invention is low, it may be purified by a method such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography or the like.

<Organic semiconductor materials>
In the present specification, the organic semiconductor material means a material (composition) having the polymer compound of the present invention and a compound different from the polymer compound of the present invention. The compound different from the polymer compound of the present invention is preferably a compound having carrier transport properties, and may be a low molecular compound or a polymer compound. Further, the polymer compound of the present invention contained in the organic semiconductor material may be one kind alone or two or more kinds. The organic semiconductor material preferably contains 30% by weight or more of the polymer compound of the present invention, and more preferably contains 50% by weight or more.

Examples of compounds having carrier transport properties include arylamine derivatives, stilbene derivatives, oligothiophene and derivatives thereof, low molecular compounds such as oxadiazole derivatives, fullerenes and derivatives thereof; polyvinylcarbazole and derivatives thereof, polyaniline and derivatives thereof , Polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and polyfluorene and derivatives thereof.

The organic semiconductor material may contain a polymer compound different from the polymer compound of the present invention as a polymer binder in order to improve its characteristics.

Specific examples of the polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof. Derivatives, polycarbonates, polyacrylates, polymethyl acrylates, polymethyl methacrylates, polystyrenes, polyvinyl chlorides, polysiloxanes.

<Organic semiconductor element>
Since the polymer compound of the present invention exhibits excellent field effect mobility, it can be suitably used for an organic layer of an organic semiconductor element. Examples of the organic semiconductor element include an organic transistor, an organic solar battery, and an organic electroluminescence element. Among these organic semiconductor elements, the polymer compound of the present invention can be particularly suitably used for an organic layer (active layer) of an organic transistor.

<Organic transistor>
Examples of the organic transistor of the present invention include a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path And a transistor having a configuration including: Examples of the organic transistor having such a configuration include a field effect organic transistor and a static induction organic transistor.

A field effect organic transistor generally includes a source electrode and a drain electrode, an active layer containing a polymer compound serving as a current path between these electrodes, a gate electrode for controlling the amount of current passing through the current path, and an active layer And an insulating layer disposed between the gate electrode and the gate electrode. In particular, a field effect organic transistor in which a source electrode and a drain electrode are provided in contact with an active layer and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween is preferable.

An electrostatic induction organic transistor usually has a source electrode and a drain electrode, an active layer containing a polymer compound serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path. The gate electrode is provided in the active layer. In particular, an electrostatic induction organic transistor in which a source electrode, a drain electrode, and the gate electrode are provided in contact with the active layer is preferable.

The gate electrode only needs to have a structure in which a current path flowing from the source electrode to the drain electrode can be formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. Type electrode.

FIG. 1 is a schematic cross-sectional view showing a configuration example of a first embodiment (field effect organic transistor) of an organic transistor of the present invention.
An organic transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the main surface of the substrate 1 so as to be separated from the substrate 1 at a predetermined interval, The active layer 2 formed on the substrate 1 so as to cover the drain electrode 6, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 on the region between the source electrode 5 and the drain electrode 6 And a gate electrode 4 formed on the insulating layer 3 so as to straddle the source electrode 5 and the drain electrode 6 when viewed from the thickness direction of the substrate 1.

FIG. 2 is a schematic cross-sectional view showing a configuration example of a second embodiment (field-effect organic transistor) of the organic transistor of the present invention.
The organic transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 and the source electrode 5 so as to cover the source electrode 5, and a source electrode 5 between the source electrode 5 and the drain electrode 6, the drain electrode 6 formed on the active layer 2 so as to be separated from the source electrode 5 by a predetermined interval, the insulating layer 3 formed on the active layer 2 and the drain electrode 6, And the gate electrode 4 formed on the insulating layer 3 so as to straddle the source electrode 5 and the drain electrode 6 when viewed from the thickness direction of the substrate 1.

FIG. 3 is a schematic cross-sectional view showing a configuration example of a third embodiment (field-effect organic transistor) of the organic transistor of the present invention.
The organic transistor 120 shown in FIG. 3 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and a gate electrode 4 The regions of the insulating layer 3 formed in the lower part are formed on the insulating layer 3 at predetermined intervals so as to partially cover the gate electrode 4 when viewed from the thickness direction of the substrate 1. The source electrode 5 and the drain electrode 6 and a part of the source electrode 5 and the drain electrode 6 are covered and formed on the insulating layer 3 so as to straddle the source electrode 5 and the drain electrode 6 when viewed from the thickness direction of the substrate 1. Active layer 2 formed.

FIG. 4 is a schematic cross-sectional view showing a configuration example of a fourth embodiment (field effect type organic transistor) of the organic transistor of the present invention.
The organic transistor 130 shown in FIG. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, a substrate 1 and an insulating layer 3 formed on the gate electrode 4 so as to cover the gate electrode 4, a substrate The source electrode 5 formed on the insulating layer 3 so as to cover a part of the region of the insulating layer 3 so as to straddle the gate electrode 4 when viewed from the thickness direction 1 and a part of the source electrode 5 are covered. In addition, the active layer 2 formed on the insulating layer 3 so as to expose a part of the insulating film 3 and the active layer 2 so as to straddle the gate electrode 4 when viewed from the thickness direction of the substrate 1. And a part of the insulating layer 3 and a source electrode 5 and a drain electrode 6 formed so as to be spaced apart at a predetermined interval.

FIG. 5 is a schematic cross-sectional view showing a configuration example of a fifth embodiment (electrostatic induction type organic transistor) of the organic transistor of the present invention.
An organic transistor 140 shown in FIG. 5 is separated from the substrate 1, the source electrode 5 formed on the substrate 1, the active layer 2 formed on the source electrode 5, and the active layer 2 at a predetermined interval. The plurality of comb-like gate electrodes 4 formed as described above, and the active layer 2 and the active layer 2a (active layer 2a) covering the gate electrode 4 so as to integrally cover all of the plurality of comb-like gate electrodes 4 May be the same as or different from the material of the active layer 2) and the active layer 2 a so as to overlap the comb-shaped gate electrode 4 when viewed from the thickness direction of the substrate 1. And a drain electrode 6 formed in a conventional manner.

FIG. 6 is a schematic cross-sectional view showing a configuration example of a sixth embodiment (field-effect organic transistor) of the organic transistor of the present invention.
The organic transistor 150 shown in FIG. 6 is on the substrate 1, the active layer 2 formed on the substrate 1, and the active layer 2, and the height of the upper surface of the active layer 2 is substantially the same as the height of the upper surface. And the source electrode 5 and the drain electrode 6 formed so as to be separated from each other at a predetermined interval, and the source electrode 5 and the drain electrode 6 so as to cover a part of the source electrode 5 and the drain electrode 6. It has an insulating layer 3 formed on the active layer 2 and a gate electrode 4 formed so as to straddle the source electrode 5 and the drain electrode 6 when viewed from the thickness direction of the substrate 1.

FIG. 7: is typical sectional drawing which shows the structural example of 7th Embodiment (field effect type organic transistor) of the organic transistor of this invention.
The organic transistor 160 shown in FIG. 7 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and a thickness of the substrate 1. The active layer 2 formed so as to cover the region on the gate electrode 4 when viewed from the direction and the gate electrode 4 so as to cover a part of the active layer 2 and viewed from the thickness direction of the substrate 1. A source electrode 5 formed on the active layer 2 so as to span a part, and a part of the gate electrode 4 so as to cover a part of the active layer 2 and when viewed from the thickness direction of the substrate 1 It has a drain electrode 6 formed on the active layer 2 so as to be separated from the source electrode 5 at a predetermined interval.

FIG. 8: is typical sectional drawing which shows the structural example of 8th Embodiment (field effect type organic transistor) of the organic transistor of this invention.
An organic transistor 170 shown in FIG. 8 includes a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, an active layer 2 formed on the insulating layer 3, and a predetermined interval on the active layer 2. It has the source electrode 5 and the drain electrode 6 which were formed so that it might space apart. In this configuration example, the gate electrode 4 also serves as the substrate 1.

FIG. 9 is a schematic cross-sectional view showing a configuration example of a ninth embodiment (field-effect organic transistor) of the organic transistor of the present invention.
The organic transistor 180 shown in FIG. 9 includes a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, and a source electrode 5 and a drain electrode formed on the insulating layer 3 so as to be spaced apart at a predetermined interval. 6 and an active layer 2 formed on the insulating layer 3 so as to straddle part of the source electrode 5 and part of the drain electrode 6.

In the above-described organic transistor of the present invention, the active layer 2 and / or the active layer 2a is composed of an organic layer containing the polymer compound of the present invention, and a current path (channel) between the source electrode 5 and the drain electrode 6 is formed. ) The gate electrode 4 controls the amount of current passing through the current path by applying a voltage.

The field effect organic transistor having the above-described configuration can be produced by a known method, for example, a method described in JP-A-5-110069. In addition, the electrostatic induction organic transistor having the above-described configuration can be manufactured by a known method such as the method described in JP-A-2004-006476.

The material of the substrate 1 is not particularly limited as long as it does not disturb the characteristics of the organic transistor. As the substrate 1, a glass substrate, a flexible film substrate, or a plastic substrate can be used.

The material of the insulating layer 3 may be any material having high electrical insulation, and SiO _x , SiN _x , Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, photoresist, or the like can be used. However, from the viewpoint of lowering the voltage, it is preferable to use a material having a high dielectric constant.

When the active layer 2 is formed on the insulating layer 3, the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. The active layer 2 may be formed after the surface modification.

In the case of a field effect organic transistor, charges such as electrons and holes generally pass near the interface between the insulating layer and the active layer. Accordingly, the state of this interface greatly affects the field effect mobility of the transistor. Therefore, as a method of improving the interface state by improving the interface state, control of the interface state by a silane coupling agent has been proposed (for example, surface chemistry, 2007, Vol. 28, No. 5, p.242). -248).

Examples of such silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, and fluorinated compounds. Examples thereof include silylamine compounds such as alkylalkoxysilanes and hexamethyldisilazane (HMDS).
In addition, the surface of the insulating layer may be subjected to ozone UV treatment or O ₂ plasma treatment before treatment with the surface treatment agent.

By such treatment, the surface energy of the silicon oxide film used as the insulating layer can be controlled. Further, the surface treatment improves the orientation of the film constituting the active layer on the insulating layer, and high charge transportability (field effect mobility) can be obtained.

Examples of the material of the gate electrode 4 include gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum, low resistance polysilicon, low resistance amorphous silicon, and other metals, tin oxide, indium oxide, and indium. Examples thereof include tin oxide (ITO). These materials may be used alone or in combination of two or more. As the gate electrode 4, it is also possible to use a silicon substrate doped with impurities at a high concentration. A silicon substrate doped with impurities at a high concentration has not only performance as a gate electrode but also performance as a substrate. When the gate electrode 4 having such a performance as a substrate is used, the substrate 1 may be omitted in the organic transistor in which the substrate 1 and the gate electrode 4 are in contact with each other.

The source electrode 5 and the drain electrode 6 are preferably made of a low resistance material, and particularly preferably made of gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum or the like. These materials may be used alone or in combination of two or more.

In the organic transistor, a layer composed of another compound may be interposed between the source electrode 5 and the drain electrode 6 and the active layer 2. Examples of such layers include low molecular compounds having electron transport properties, low molecular compounds having hole transport properties, alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, iodine, bromine, Halogens such as chlorine and iodine chloride, sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide and sulfate, nitric oxide compounds such as nitric acid, nitrogen dioxide and nitrate, halogenated compounds such as perchloric acid and hypochlorous acid, Examples thereof include layers made of aromatic thiol compounds such as alkyl thiol compounds, aromatic thiols, and fluorinated alkyl aromatic thiols.

In addition, after manufacturing the organic transistor as described above, it is preferable to form a protective film on the organic transistor in order to protect the organic transistor. Thereby, an organic transistor is interrupted | blocked from air | atmosphere and the fall of the electrical property of an organic transistor can be suppressed. Further, when a display device driven by the organic transistor is further formed on the organic transistor, the protective film can also reduce the influence on the organic transistor in the forming process.

Examples of the method for forming the protective film include a method of covering the organic transistor with a film of an inorganic material such as a UV curable resin, a thermosetting resin, or a SiON _X film. In order to effectively block the atmosphere, it is preferable to form a protective film after the organic transistor is manufactured without exposing the organic transistor to the atmosphere (for example, in a dry nitrogen gas atmosphere or in a vacuum).

A field effect organic transistor, which is a kind of organic transistor configured as described above, can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display. And the field effect type organic transistor of embodiment mentioned above contains the high molecular compound of this invention as an active layer, Therefore, it has an active layer with improved charge transport property. Therefore, since the field effect mobility of the field effect organic transistor can be increased, the field effect organic transistor of the present invention is useful for manufacturing a display having a sufficient response speed.

Hereinafter, examples will be shown to describe the present invention in more detail, but the present invention is not limited to these examples.

(NMR analysis)
The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (manufactured by Varian).

(Molecular weight analysis)
The number average molecular weight and weight average molecular weight of the polymer compound were determined using gel permeation chromatography (GPC, manufactured by Tosoh Corporation). The polymer compound to be measured was dissolved in orthodichlorobenzene and injected into GPC. Orthodichlorobenzene was used for the mobile phase of GPC. The column used was TSKgel GMHHR-H (S) HT (two linked, manufactured by Tosoh Corporation). A UV detector was used as the detector.

(Synthesis Example 1: Synthesis of Compound 3)
Compound 3 was synthesized according to the following scheme.

To the reaction vessel, sodium cyanide (53.5 g, 1.09 mol) and distilled water (85 mL) were added and heated for 15 minutes until the sodium cyanide was dissolved. Subsequently, methanol was added to the reaction solution and refluxed. Further, Compound 2 (70.9 g, 0.36 mol) was added to the reaction solution, and then a mixture of Compound 1 (80.0 g, 0.432 mol) and Compound 2 (44.0 g, 0.224 mmol) was added to the reaction solution. Dropped and refluxed for 30 minutes. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was collected by filtration, washed in turn with a 75% aqueous methanol solution, water and diethyl ether, and then recrystallized using a dichloromethane-methanol mixed solvent to give compound 3 Was obtained as a colorless solid. The yield of compound 3 was 72.8 g, and the yield was 43%. The measured ¹ H-NMR results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.22 (s, 2H), 7.25 (d, 4H), 7.55 (d, 4H).

(Synthesis Example 2: Synthesis of Compound 4)
Compound 4 was synthesized according to the following scheme.

To the reaction vessel, compound 3 (39 g, 0.100 mol), concentrated sulfuric acid (175 mL), distilled water (200 mL) and acetic acid (250 mL) were added and refluxed for 24 hours. After completion of the reaction, the reaction solution was diluted with water, and the precipitated solid was collected by filtration to obtain Compound 4. The yield of compound 4 was 25.6 g, and the yield was 60%.

(Synthesis Example 3: Synthesis of Compound 5)
Compound 5 was synthesized according to the following scheme.

Concentrated sulfuric acid (685 g) was added to the reaction vessel and stirred at room temperature. Compound 4 (25 g, 58.4 mmol) was added to the reaction solution little by little at room temperature, followed by stirring at 100 ° C. for 2 hours. After completion of the reaction, the reaction solution was poured onto ice and the precipitated solid was collected by filtration. The obtained solid was washed with water and dried under vacuum to obtain a crude product. The obtained crude product was purified by column chromatography to obtain compound 5. The yield of compound 5 was 5.95 g, and the yield was 26%. The measured ¹ H-NMR results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.37 (s, 2H), 7.79 (d, 4H), 7.84 (s, 2H).

(Synthesis Example 4: Synthesis of Compound 6)
Compound 6 was synthesized according to the following scheme.

After replacing the gas in the reaction vessel with argon gas, magnesium (0.615 g, 25 mmol) and THF (20 mL) were added and stirred while refluxing. A Grignard reagent was synthesized by adding dropwise a solution of 2-bromo-5-hexadecylthiophene (2.35 g, 7.6 mmol) in THF (10 mL) to the obtained THF solution and stirring for 1 hour at reflux. After replacing the gas in another flask with argon gas, Compound 5 (0.823 g, 2.1 mmol) and THF (20 mL) were added, and then the obtained Grignard reagent was added dropwise at 0 ° C. at room temperature. Stir for 3 hours. After completion of the reaction, the reaction solution was poured into a mixed solution of ice and hydrochloric acid, extracted with ethyl acetate, and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in methanol (100 mL), 2N hydrochloric acid (2.5 mL) was added, and the mixture was stirred for 3 hr while refluxing. After completion of the reaction, water was added and the precipitated solid was collected by filtration. The obtained solid was recrystallized with a mixed solvent of chloroform-methanol to obtain Compound 6. The yield of compound 6 was 1.21 g, and the yield was 60%. The measured ¹ H-NMR results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.88 (t, 6H), 1.26 (m, 26H), 1.75 (quint, 4H), 2.90 (t, 4H) ), 6.90 (d, 2H), 7.08 (dd, 2H), 7.31 (d, 2H), 7.44 (s, 2H), 7.51 (d, 2H).

(Example 1: Synthesis of polymer compound A)
Polymer compound A was synthesized according to the following scheme.

In a pressure vessel for a microwave reactor, toluene (5 mL), dichlorobis (triphenylphosphine) palladium (II) (2.9 mg, 0.025 mmol), compound 6 (97.3 mg, 0.1 mmol), and compound 7 (49.1 mg, 0.1 mmol) was added, and the pressure vessel was filled with argon gas and sealed. The pressure vessel was heated by microwave at 180 ° C. for 40 minutes. After completion of the reaction, the reaction solution was cooled to room temperature and then poured into a mixed solution of methanol (100 mL) and hydrochloric acid (2 mL) and stirred for 5 hours. The deposited precipitate was collected by filtration, washed with methanol, hexane and chloroform in this order, and then extracted with chlorobenzene. The obtained chlorobenzene solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain polymer compound A (39.2 mg). The obtained polymer compound A had a polystyrene-equivalent number average molecular weight of 2.0 × 10 ⁴ and a weight average molecular weight of 4.3 × 10 ⁴ .

(Synthesis Example 5: Synthesis of Compound 8)
Compound 8 was synthesized according to the following scheme.

After replacing the gas in the reaction vessel with argon gas, magnesium (0.615 g, 25 mmol) and THF (20 mL) were added and stirred while refluxing. A Grignard reagent was synthesized by adding dropwise a solution of 2-bromo-5-octyldodecylthiophene (2.8 g, 7.6 mmol) in THF (10 mL) to the obtained THF solution and stirring for 1 hour at reflux. After replacing the gas in another flask with argon gas, Compound 5 (0.823 g, 2.1 mmol) and THF (20 mL) were added, and then the obtained Grignard reagent was added dropwise at 0 ° C. at room temperature. Stir for 3 hours. After completion of the reaction, the reaction solution was poured into a mixed solution of ice and hydrochloric acid, extracted with ethyl acetate, and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in methanol (100 mL), 2N hydrochloric acid (2.5 mL) was added, and the mixture was stirred for 3 hr while refluxing. After completion of the reaction, water was added and the precipitated solid was collected by filtration. The obtained solid was recrystallized with a mixed solvent of chloroform-methanol to obtain Compound 8. The yield of compound 8 was 1.13 g, and the yield was 51%. The measured ¹ H-NMR results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 0.87 (t, 12H), 1.26-1.33 (m, 62H), 1.70 (m, 2H), 2.83 (D, 4H), 6.85 (d, 2H), 7.07 (dd, 2H), 7.30 (d, 2H), 7.43 (s, 2H), 7.51 (d, 2H) .

(Example 2: Synthesis of polymer compound B)
Polymer compound B was synthesized according to the following scheme.

In a pressure vessel for a microwave reactor, toluene (5 mL), dichlorobis (triphenylphosphine) palladium (II) (2.9 mg, 0.025 mmol), compound 8 (0.109 mg, 0.1 mmol), and compound 7 (49.1 mg, 0.1 mmol) was added, and the pressure vessel was filled with argon gas and sealed. The pressure vessel was heated by microwave at 180 ° C. for 40 minutes. After completion of the reaction, the reaction solution was cooled to room temperature and then poured into a mixed solution of methanol (100 mL) and hydrochloric acid (2 mL) and stirred for 5 hours. The deposited precipitate was collected by filtration, washed with methanol and hexane in order, and then extracted with chloroform. The obtained chloroform solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain polymer compound B (98.2 mg). The obtained polymer compound B had a polystyrene-equivalent number average molecular weight of 1.8 × 10 ⁴ and a weight average molecular weight of 4.1 × 10 ⁴ .

(Example 3: Production and evaluation of organic transistor (1))
An organic transistor having the structure already described with reference to FIG. 8 was prepared using the polymer compound A, and the transistor characteristics were measured. That is, first, the surface of the n-type silicon substrate 4 doped with impurities at a high concentration serving as a gate electrode was thermally oxidized to form a silicon oxide film 3 having a thickness of 200 nm. After thoroughly cleaning this substrate, the surface of the substrate was treated with silane using 1H, 1H, 2H, 2H-perfluorodecyltriethoxychlorosilane (FDTS).

Next, the polymer compound A was dissolved in orthodichlorobenzene to prepare a 3 g / L solution, which was filtered through a membrane filter. Using the obtained solution, a thin film (organic semiconductor layer 2) containing the polymer compound A having a thickness of about 30 nm was formed on the surface-treated substrate by spin coating. This thin film was heated at 150 ° C. for 30 minutes in a nitrogen gas atmosphere. Then, a source electrode 5 and a drain electrode 6 having a channel length of 50 μm and a channel width of 1.5 mm were produced on the obtained thin film by vacuum deposition to obtain an organic transistor (1).

With respect to this organic transistor, the transistor characteristics were measured by changing the gate voltage Vg from 40 V to −60 V and the source-drain voltage Vsd from 0 V to −60 V. From this result, the field effect mobility was calculated to be 0.19 cm ² / Vs.

(Example 4: Production and evaluation of organic transistor (2))
An organic transistor having the structure already described with reference to FIG. 8 was prepared using the polymer compound B, and the transistor characteristics were measured. That is, first, the surface of the n-type silicon substrate 4 doped with an impurity serving as a gate electrode at a high concentration was thermally oxidized to form a silicon oxide film 3 having a thickness of 200 nm. After thoroughly washing the substrate, the substrate surface was silane treated with hexamethylene disilazane (HMDS).

Next, the polymer compound B was dissolved in orthodichlorobenzene to prepare a 3 g / L solution, which was filtered through a membrane filter. Using the obtained solution, a thin film (organic semiconductor layer 2) containing the polymer compound B having a thickness of about 30 nm was formed on the surface-treated substrate by spin coating. This thin film was heated at 150 ° C. for 30 minutes in a nitrogen gas atmosphere. Then, a source electrode 5 and a drain electrode 6 having a channel length of 50 μm and a channel width of 1.5 mm were produced on the obtained thin film by vacuum vapor deposition to obtain an organic transistor (2).

With respect to this organic transistor, the transistor characteristics were measured by changing the gate voltage Vg from 40 V to −60 V and the source-drain voltage Vsd from 0 V to −60 V. From this result, the field effect mobility was calculated to be 9.3 × 10 ⁻² cm ² / Vs.

(Example 5: Production and evaluation of organic transistor (3))
An organic transistor having the structure already described with reference to FIG. 8 was prepared using the polymer compound B, and the transistor characteristics were measured. That is, first, the surface of the n-type silicon substrate 4 doped with an impurity serving as a gate electrode at a high concentration was thermally oxidized to form a silicon oxide film 3 having a thickness of 200 nm. After sufficiently washing the substrate, the surface of the substrate was treated with silane using FDTS.

Next, the polymer compound B was dissolved in orthodichlorobenzene to prepare a 3 g / L solution, which was filtered through a membrane filter. Using the obtained solution, a thin film (organic semiconductor layer 2) containing the polymer compound B having a thickness of about 30 nm was formed on the surface-treated substrate by spin coating. Then, a source electrode 5 and a drain electrode 6 having a channel length of 50 μm and a channel width of 1.5 mm were produced on the obtained thin film by vacuum deposition to obtain an organic transistor (3).

With respect to this organic transistor, the transistor characteristics were measured by changing the gate voltage Vg from 40 V to −60 V and the source-drain voltage Vsd from 0 V to −60 V. From this result, the field effect mobility was calculated to be 0.15 cm ² / Vs.

(Synthesis Example 6: Synthesis of polymer compound C)
According to the following scheme, polymer compound C, which has been conventionally used as a material for the active layer of an organic transistor, was synthesized.

Using a four-necked flask, compound 8 (97.2 mg, 0.300 mmol), compound 9 (159.4 mg, 0.270 mmol), toluene (10 mL) and methyltrialkylammonium chloride (trade name Aliquat 336®) Aldrich) (60.6 mg, 0.15 mmol) was added, and argon bubbling was performed at room temperature (25 ° C.) for 30 minutes.

After the temperature of this solution was raised to 90 ° C., palladium acetate (0.67 mg, 1 mol%) and tris (2-methoxyphenyl) phosphine (3.70 mg, 3.5 mol%) were added. Thereafter, an aqueous sodium carbonate solution (16.7 wt%, 1.90 g, 3.00 mmol) was added dropwise over 30 minutes while stirring at 100 ° C. After 4 hours, phenylboronic acid (3.66 mg, 0.03 mmol), palladium acetate (0.67 mg, 1 mol%) and tris (2-methoxyphenyl) phosphine (3.70 mg, 3.5 mol%) were added, and After stirring for 1 hour, the reaction was stopped. The reaction was performed in an argon gas atmosphere.

Thereafter, sodium diethyldithiocarbamate (1 g) and pure water (10 mL) were added to the solution after the reaction, followed by stirring while refluxing for 1 hour. After removing the aqueous layer in the obtained reaction solution, the organic layer was washed twice with 10 mL of water, twice with 10 mL of acetic acid aqueous solution (3% by weight), and further twice with 10 mL of water, poured into methanol, and polymer compound. Was precipitated.

The obtained polymer compound was filtered and dried, and then the polymer compound was redissolved in toluene (15 mL) and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer compound, filtered, and dried to obtain 69 mg of polymer compound C.

(Comparative Example 1: Production and evaluation of organic transistor 4)
An organic transistor having the structure already described with reference to FIG. 8 was prepared using the polymer compound C, and the transistor characteristics were measured. That is, first, the surface of the n-type silicon substrate 4 doped with an impurity serving as a gate electrode at a high concentration was thermally oxidized to form a silicon oxide film 3 having a thickness of 200 nm. The substrate was ultrasonically cleaned with acetone for 10 minutes and then irradiated with ozone UV for 20 minutes. Thereafter, silane treatment was performed on the substrate surface by spin coating using β-phenethyltrichlorosilane (β-PTS).

Next, the polymer compound C was dissolved in chloroform as a solvent to prepare a solution having a total concentration of 0.5% by weight, and this was filtered through a membrane filter. Using the obtained solution, a thin film (organic semiconductor layer 2) of polymer compound C having a thickness of about 60 nm was formed on the surface-treated substrate by spin coating. Then, a source electrode 5 and a drain electrode 6 having a channel length of 20 μm and a channel width of 2 mm (MoO ₃ , gold in order from the thin film side) are formed on the obtained thin film by a vacuum deposition method using a metal mask. Electrode having a laminated structure of 2) was produced to obtain an organic transistor.

For this organic transistor, the transistor characteristics were measured by changing the gate voltage Vg from 10 V to -50 V and the source-drain voltage Vsd from 0 V to -50 V. As a result, a drain current of 0.54 μA was obtained when the transfer characteristics were Vg = −50 V and Vsd = −50 V. From this result, the field effect mobility was calculated to be 0.0015 cm ² / Vs, and it was confirmed that the field effect mobility was lower than that of the organic transistor prepared using the polymer compounds A to B.

DESCRIPTION OF SYMBOLS 1

Substrate

2, 2a Active layer 3 Insulating layer 4 Gate electrode 5 Source electrode 6

Drain electrode

100, 110, 120, 130, 140, 150, 160, 170, 180 Organic transistor

Claims

The high molecular compound containing the structural unit represented by following formula (1).

(In the formula (1),
A ring and B ring each independently represent an aromatic hydrocarbon ring or a heterocyclic ring.
R 1 is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group Represents an acyloxy group, an amide group, a carboxy group, a nitro group or a cyano group, and these groups optionally have a substituent. Two R 1 may be different from each other. )
The polymer compound according to claim 1, wherein both the A ring and the B ring are the same aromatic hydrocarbon ring or heterocyclic ring.
The polymer compound according to claim 1, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (2).

(In the formula (2),
R 1 represents the same meaning as described above.
X represents a group represented by ═CR 2 — and a group represented by ═N—. A plurality of Xs may be different from each other. R 2 is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group Represents an acyloxy group, an amide group, a carboxy group, a nitro group or a cyano group, and these groups optionally have a substituent. )
4. The polymer compound according to claim 3, wherein a plurality of Xs are all groups represented by ═CR 2 —.
The polymer compound according to claim 1, further comprising a structural unit represented by the following formula (3).

(In formula (3),
Y represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. )
An organic semiconductor material comprising the polymer compound according to claim 1.
An organic semiconductor element having an organic layer containing the organic semiconductor material according to claim 6.
An organic transistor having a source electrode, a drain electrode, a gate electrode, and an active layer, wherein the active layer includes the organic semiconductor material according to claim 6.