JP2012004192A - Organic transistor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic transistor having high mobility, a large current on/off ratio, and excellent in storage stability.SOLUTION: The organic transistor has an organic semiconductor layer which contains at least two structural units represented by a formula (1)(in the formula, Xand Xeach independently denote a hydrogen atom, a halogen atom, straight-chain, branched or cyclic alkyl, straight-chain, branched or cyclic alkoxy, straight-chain, branched or cyclic alkoxyalkyl or substituted or unsubstituted aryl; at least two structural units are identical or different) in one group of repeating units, and at least one structural unit represented by a formula (2),-Ar-(2);(in the formula, Ar represents substituted or unsubstituted arylene, if structural units are more than two, structural units are identical or different), and at least one kind of oligomer or polymer having the repeating number of repeating units, formed by the structural units represented by the formula (1) and (2), of 1-10000.

Description

The present invention relates to an organic transistor. More specifically, the present invention relates to an organic transistor using an organic compound having a specific structure for an organic semiconductor layer.

Conventionally, a thin film transistor (TFT) made of amorphous silicon or polycrystalline silicon has been widely used as a switching element for flat panel display such as a liquid crystal display device. However, a CVD apparatus used for manufacturing a thin film transistor using silicon is expensive, and manufacturing a large-sized thin film transistor element has a drawback of increasing manufacturing cost.
In addition, since amorphous silicon and polycrystalline silicon are formed at a high temperature, there is a problem that a plastic material that is lightweight and flexible but has poor heat resistance cannot be used as a substrate. .
In order to solve the above problem, an organic transistor (also referred to as an organic thin film transistor or an organic TFT) using an organic compound for a channel semiconductor layer (hereinafter referred to as an organic semiconductor layer) instead of amorphous silicon or polycrystalline silicon is proposed. (Non-Patent Document 1).

As a method for forming the organic semiconductor layer, for example, a vacuum deposition method or a coating method is known. According to these film formation methods, it is easy to increase the size of the organic transistor element while suppressing the manufacturing cost. .
Furthermore, the temperature required for film formation can be lowered, and organic transistors using organic compounds can use plastic materials for the substrate, which can be applied to flexible display elements. Expectations are gathered for the transformation.

A practical organic transistor needs to have characteristics such as high charge mobility and a large current on / off ratio. Here, the term “on / off ratio” means the ratio of the current between the source electrode and the drain electrode when the organic transistor is on to the current between the source electrode and the drain electrode when the organic transistor is off. To do.
Furthermore, excellent storage stability is required for practical application of organic transistors.

To date, organic transistors using, for example, pentacene as the organic semiconductor layer have been proposed (Non-Patent Document 2).
However, an organic transistor using pentacene has a problem that it has a low function as an organic transistor in the atmosphere and low storage stability.
Furthermore, an organic transistor using a thiophene oligomer (α-hexathienylene) as an organic semiconductor layer has been proposed (Non-patent Document 3). However, the organic transistor also has a drawback that its storage stability in air is low.
In addition, when using these compounds for an organic-semiconductor layer, the layer is formed by the vacuum evaporation method (dry process).

For example, polythiophene compounds have been proposed for forming an organic semiconductor layer by a coating method (wet process) in a state of being dissolved or dispersed in a solvent (Patent Documents 1 and 2). However, it cannot be said that the charge mobility of an organic transistor using a polythiophene compound for the organic semiconductor layer is sufficiently high, and the storage stability in air is not sufficient.
At present, development of further improved organic transistors is required for practical use.

JP 2003-221434 A JP 2003-261655 A

Appl. Phys. Lett. 63, 1372 (1993) Appl. Phys. Lett. , 72, 1854 (1998) Science, 268, 270 (1995)

To date, organic transistors using various organic compounds as organic semiconductor layers have been proposed, but none of them has practically satisfactory characteristics. .
In view of the above, the present invention is to provide an organic transistor having high charge mobility, a large current on / off ratio, and excellent storage stability.
Even when an organic semiconductor layer is formed by a coating method (wet process) in a state dissolved or dispersed in a solvent, it has a high charge mobility, a large current on / off ratio, and excellent storage stability. An organic transistor is provided.

（式中、Ｘ_１およびＸ_２はそれぞれ独立に、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基、あるいは置換または未置換のアリール基を表し、２つ以上の該構造単位は、同一の基であっても、異なる基であってもよい）
且つ、
式（２）で表される構造単位を少なくとも１つ含有し、
−Ａｒ− （２）
（式中、Ａｒは、置換または未置換のアリーレン基を表し、該構造単位が２つ以上の場合は、同一の基であっても、異なる基であってもよい）
式（１）および式（２）で表される構造単位から成る繰り返し単位の繰り返し数が１〜１００００であるオリゴマーまたはポリマーを少なくとも１種含有してなる有機トランジスタである。
As a result of intensive studies to solve the above problems, the inventor of the present invention has an organic transistor containing an oligomer or polymer having a specific structure in an organic semiconductor layer, and has a high charge mobility and a large current on / off ratio. It has been found that it has excellent storage stability, and the present invention has been completed.
That is, the present invention
(I) In an organic transistor having an organic semiconductor layer, the organic semiconductor layer includes:
In one repeating unit, at least two structural units represented by the formula (1) are contained,

Wherein X ₁ and X ₂ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group Or a substituted or unsubstituted aryl group, and two or more structural units may be the same group or different groups)
and,
Containing at least one structural unit represented by formula (2),
-Ar- (2)
(In the formula, Ar represents a substituted or unsubstituted arylene group, and when there are two or more structural units, they may be the same group or different groups)
An organic transistor comprising at least one oligomer or polymer in which the number of repeating units composed of structural units represented by formula (1) and formula (2) is 1 to 10,000.

According to the present invention, it is possible to provide an organic transistor having a high charge mobility, a large current on / off ratio, and excellent storage stability.

It is typical sectional drawing of the organic transistor of this invention. It is typical sectional drawing of the organic transistor of this invention. It is typical sectional drawing of the organic transistor of this invention. It is typical sectional drawing of the organic transistor of this invention.

（式中、Ｘ_１およびＸ_２はそれぞれ独立に、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基、あるいは置換または未置換のアリール基を表し、２つ以上の該構造単位は、同一の基であっても、異なる基であってもよい）
且つ、
式（２）で表される構造単位を少なくとも１つ含有し、
−Ａｒ− （２）
（式中、Ａｒは、置換または未置換のアリーレン基を表し、該構造単位が２つ以上の場合は、同一の基であっても、異なる基であってもよい）
式（１）および式（２）で表される構造単位から成る繰り返し単位の繰り返し数が１〜１００００であるオリゴマーまたはポリマーを少なくとも１種含有してなる。

本発明に係る１つの繰り返し単位中に、式（１）で表される構造単位を少なくとも２つ有し、且つ、式（２）で表される構造単位少なくとも一つ有して成り、その繰り返し単位の繰り返し数が１〜１００００であるオリゴマーまたはポリマーを、以下、本発明に係る化合物Ａと略記する。
Hereinafter, the present invention will be described in detail.
In the organic transistor of the present invention, the organic semiconductor layer includes
In one repeating unit, at least two structural units represented by the formula (1) are contained,

Wherein X ₁ and X ₂ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group Or a substituted or unsubstituted aryl group, and two or more structural units may be the same group or different groups)
and,
Containing at least one structural unit represented by formula (2),
-Ar- (2)
(In the formula, Ar represents a substituted or unsubstituted arylene group, and when there are two or more structural units, they may be the same group or different groups)
It comprises at least one oligomer or polymer in which the number of repeating units composed of the structural units represented by formula (1) and formula (2) is 1 to 10,000.

One repeating unit according to the present invention has at least two structural units represented by the formula (1) and at least one structural unit represented by the formula (2). Hereinafter, an oligomer or polymer having 1 to 10,000 repeating units is abbreviated as Compound A according to the present invention.

In the structural unit represented by the formula (1), X ₁ and X ₂ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, and a linear chain Represents a branched or cyclic alkoxyalkyl group, or a substituted or unsubstituted aryl group.
In the present specification, the aryl group represents a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group. In addition, the substituent of the aryl group includes a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a carbon number of 4 to The aryl group which may be substituted by 20 said halogen atoms, an alkyl group, and an alkoxy group etc. are mentioned.

In the structural unit represented by the formula (1), X ₁ and X ₂ are more preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a C ₁ to 20 carbon atom. A linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 4 to 20 carbon atoms is represented.

Specific examples of X ₁ and X ₂ in formula (1) include, for example, a hydrogen atom; for example, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4- Methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 1-methylheptyl group 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4- Ptyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl Linear, branched or cyclic alkyl groups such as groups;
For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n -Undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyl group Linear, branched or cyclic alkoxy groups such as oxy group and n-eicosyloxy group

For example, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-heptyloxymethyl group, n-octyl Oxymethyl group, n-decyloxymethyl group, n-dodecyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxy Ethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group Group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-n-pentyloxypropyl group, 3-n-hexyloxypropyl group, 3- (2′-ethylbutoxy) propyl group, 3-n-octyloxypropyl group, 3- ( 2'-ethylhexyloxy) propyl group, 3-n-decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butyl group Xylbutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group 5-n-propoxypentyl group, 5-n-pentyloxypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyl Oxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 8-ethoxyoctyl group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxydecyl group, 10-ethoxyde Group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 11-ethoxyundecyl group, 12-methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, 14-methoxytetradecyl group A linear, branched or cyclic alkoxyalkyl group such as a tetrahydrofurfuryl group;

For example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl Group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4-n-dodecylphenyl group 4-n-tetradecylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethyl An phenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,5,6-tetramethylphenyl group, 5-indanyl group, 1,2,3,4-tetrahydro-5-naphthyl group, 1,2,3,4-tetrahydro-6-naphthyl group,
2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxy Phenyl group, 4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxy Phenyl group, 4-n-nonyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-undecyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 2-methoxy-4-methylphenyl group, 2-methoxy-5-methylphenyl group, 2-methyl- 4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group,
2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 3-trifluoromethylphenyl group, 4-triphenyl Fluoromethylphenyl group, 2,4-difluorophenyl group, 2,4-dichlorophenyl group, 3,4-difluorophenyl group, 3,4-dichlorophenyl group, 3,5-difluorophenyl group, 3,5-dichlorophenyl group, 3,4,5-trifluorophenyl group, 2-methyl-4-chlorophenyl group, 2-chloro-4-methylphenyl group, 3-chloro-4-methylphenyl group, 2-chloro-4-methoxyphenyl group, 3-methoxy-4-fluorophenyl group, 3-methoxy-4-chlorophenyl group, 3-fluoro-4 Methoxyphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-methoxy) Phenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-ethoxy-1-naphthyl group, 6-n-butyl-2-naphthyl group, 6-methoxy-2- Naphthyl group, 7-ethoxy-2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-tetracenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9, 9-di-n-propyl-2-fluorenyl group, 2-furyl group, 2-thienyl group, 5-n-propyl-2-thienyl group, 5-n-butyl-2-thienyl group, 5- n-hexyl-2-thienyl group, 5-n-octyl-thienyl group, 5-n-decyl-2-thienyl group, 5-n-tridecyl-2-thienyl group, 5-phenyl-2-thienyl group, 5 -(2'-thienyl) -2-thienyl group, 5- (5'-n-butyl-2'-thienyl) -2-thienyl group, 5- (5'-n-hexyl-2'-thienyl)- 2-thienyl group, 5- (5′-n-decyl-2′-thienyl) -2-thienyl group, 3-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc. A substituted aryl group can be mentioned.

In Formula (1), X ₁ and X ₂ are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a straight chain having 1 to 16 carbon atoms, a branched or cyclic alkyl group, a straight chain having 1 to 16 carbon atoms, A branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group having 2 to 16 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom.

The structural unit represented by the formula (1) is preferably a structure represented by the general formula (1-A) to the general formula (1-D), more preferably the general formula in consideration of the bond. It is a structure represented by (1-A) or general formula (1-B).

〔式中、Ｘ_１およびＸ_２は一般式（１）の場合と同じ意味を表す〕

本発明に係る化合物Ａにおいて、一つの繰り返し単位中、式（１）で表される構造単位は２つ以上含有しており、この場合、式（１）で表される構造単位は同一の構造でもよく、また異なる構造であってもよい。
式（２）で表される構造単位において、Ａｒは置換または未置換のアリーレン基を表し、該アリーレン基としては、好ましくは、環の構成炭素数が６〜２０の２価の炭素環式芳香族基、あるいは環の構成炭素数が２〜１２の２価の複素環式芳香族基である。

[Wherein, X ₁ and X ₂ represent the same meaning as in the general formula (1)]

In the compound A according to the present invention, two or more structural units represented by the formula (1) are contained in one repeating unit. In this case, the structural units represented by the formula (1) have the same structure. It may be a different structure.
In the structural unit represented by the formula (2), Ar represents a substituted or unsubstituted arylene group, and the arylene group is preferably a divalent carbocyclic aromatic having 6 to 20 carbon atoms in the ring. Or a divalent heterocyclic aromatic group having 2 to 12 carbon atoms in the ring.

  Examples of the arylene group represented by Ar include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 3,3′-biphenylene group, 3,4′-biphenylene group, 4 , 4′-biphenylene group, 9H-fluorene-2,7-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group, anthracene-2,6 -Diyl group, anthracene-9,10-diyl group, phenanthrene-1,8-diyl group, phenanthrene-9,10-diyl group, tetracene-2,8-diyl group, tetracene-5,12-diyl group, pyrene -1,6-diyl group, perylene-3,9-diyl group, carbocyclic aromatic group such as perylene-3,10-diyl group,

For example, thiophene-2,5-diyl group, 2,2′-bithiophene-5,5′-diyl group, thieno [2,3-b] thiophene-2,5-diyl group, thieno [3,2-b ] Thiophene-2,5-diyl group, dithieno [3,2-b: 2 ′, 3′-d] thiophene-2,6-diyl group, dithieno [2,3-b: 3 ′, 2′-d] ] Thiophen-2,6-diyl group, benzo [1,2-b: 4,5-b ′] dithiophene-2,5-diyl group, benzo [1,2-b: 5,4-b ′] dithiophene -2,5-diyl group, dibenzofuran-2,8-diyl group, dibenzothiophene-2,8-diyl group, dibenzothiophene-3,7-diyl group, 9H-carbazole-2,7-diyl group, 9H-carbazole 3,6-diyl group, 10H-phenoxazine-3,7-diyl group 10H- phenothiazine-3,7-diyl group,

Oxazole-2,5-diyl group, thiazole-2,5-diyl group, 1,3,4-oxadiazole-2,5-diyl group, oxazolo [5,4-d] oxazole-2,5-diyl Group, thiazolo [5,4-d] thiazole-2,5-diyl group, benzo [2,1,3] thiadiazole-4,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5 -Diyl group, pyrazine-2,5-diyl group, quinoline-2,6-diyl group, quinoxaline-2,3-diyl group, quinoxaline-2,6-diyl group, anthrazolin-2,7-diyl group, etc. Mention may be made of heterocyclic aromatic groups.

The arylene group represented by Ar may have a substituent, for example, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic group. It may be substituted with an alkoxyalkyl group or a substituted or unsubstituted aryl group.

As a specific example of the substituent which may be substituted on the arylene group, more preferably, a halogen atom exemplified as X ₁ and X ₂ in the formula (1), a linear, branched or cyclic group having 1 to 20 carbon atoms An alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 4 to 20 carbon atoms Can be illustrated.

In the structural unit represented by the formula (2), the arylene group represented by Ar is more preferably an arylene group represented by the formula (A-1) to the formula (A-12), and more preferably Is the formula (A-3), formula (A-4), formula (A-6), formula (A-7), formula (A-8), formula (A-9) or formula (A-10) An arylene group represented by formula (A-3), particularly preferably represented by formula (A-3), formula (A-6), formula (A-7), formula (A-8) or formula (A-9). An arylene group.

（式中、Ｒ_１〜Ｒ_６０はそれぞれ独立に、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基、あるいは置換または未置換のアリール基を表す）

Wherein R _{1 to} R ₆₀ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group. Or a substituted or unsubstituted aryl group)

In the compound A according to the present invention, one repeating unit contains at least one structural unit represented by the formula (2), and when two or more structural units are contained, the structural unit represented by the formula (2) The structural units may have the same structure or different structures.

The compound A according to the present invention contains at least two structural units represented by the formula (1) and at least one structural unit represented by the formula (2) in one repeating unit. The number of repeating units is 1 to 10,000.

As the compound A according to the present invention, the number average molecular weight (Mn) is about 550 to about 300000, the weight average molecular weight (Mw) is about 550 to about 1000000, and more preferably, the number average molecular weight is The weight average molecular weight is about 600 to about 500,000.

The compound A according to the present invention is more preferably an oligomer or polymer represented by the general formula (3).
R ₀ -[(A) _a- (B) _b- (C) _c- (D) _d ] _n -R ₀₀ (3)
[Wherein, A and C represent a structural unit represented by the formula (1), B and D represent a structural unit represented by the formula (2), and a, b, c and d are 0 1 or an integer of 2 or more (provided that the sum of a and c represents an integer of 2 or more, the sum of b and d represents an integer of 1 or more), n represents an integer of 1 to 10,000, R ₀ and R ₀₀ are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group, a substituted or unsubstituted aryl group Or represents a reactive group)

In the oligomer or polymer represented by the general formula (3), a halogen atom represented by R ₀ and R ₀₀ , a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, linear or branched or cyclic alkoxyalkyl group, specific examples of the substituted or unsubstituted aryl group, preferably exemplified halogen atom in X ₁ and X ₂ in the formula (1), straight-chain having 1 to 20 carbon atoms, branched or A cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted group having 4 to 20 carbon atoms An aryl group can be illustrated.

The reactive groups represented by R ₀ and R ₀₀ are groups that are reactive during oligomerization or polymerization, and are effective for Suzuki coupling reactions such as —B (OH) _2. Examples thereof include a tin-containing group effective for a Stille coupling reaction such as a boron-containing group, for example, a trialkyltin group (hereinafter referred to as “—SnR ₃ ”, R means an alkyl group).

These reactive groups may be produced, for example, by an aryl halide (for example, iodobenzene, 4-alkylbromobenzene) or a palladium catalyst [for example, bis (triphenyl) after or during the production of the oligomer or polymer. It can be converted to a non-reactive substituent such as an aryl group by acting in the presence of (phosphine) palladium chloride] and a base.

In the compound A according to the present invention, when the number of repeating units is 2 or more, one repeating unit and the other repeating units may be the same or different.
If they are different, at least one of the structural unit represented by formula (1) and the structural unit represented by formula (2) has a different structure, or the number of structural units represented by formula (1). And the case where the number of structural units represented by the formula (2) is different from each other, the case where both are different is included.

The compound A according to the present invention represents a homo-oligomer, a co-oligomer, a homopolymer and a copolymer, and includes, for example, a random co-oligomer, an alternating co-oligomer, a block co-oligomer, a random copolymer, an alternating copolymer and a block copolymer.

The oligomer or polymer represented by the general formula (3) will be described as an example. As a monomer sequence, for example, -ABBBCBBDABD or -AB- A random co-oligomer having a sequence such as A-A-C-, a random copolymer,
Moreover, as a monomer sequence, for example, an alternating co-oligomer, an alternating copolymer having a sequence such as -A-B-C-D-A-B-C-D-,
Furthermore, a block co-oligomer and a block copolymer having a sequence such as -A-A-B-B-B-C-C-C-C-D-D- as a monomer sequence are included.

In the organic transistor of the present invention, the organic semiconductor layer contains at least two structural units represented by the formula (1) in one repeating unit, and includes the structural unit represented by the formula (2). It is characterized by containing at least one oligomer or polymer containing at least one, and this makes it possible to have a high charge mobility, a large current on / off ratio, and storage stability, which has never been seen before. It is possible to provide an organic transistor excellent in the above.

As the compound A according to the present invention, for example, oligomers or polymers represented by the general formula (1-a) to the general formula (6-a) can be mentioned as preferable examples, but the present invention is limited to these. It is not something.
The compound A according to the present invention is more preferably an oligomer or polymer represented by the general formula (3-a) or the general formula (4-a).

In the structures represented by general formula (1-a) to general formula (6-a), Ar ₁ and Ar ₂ each independently represent an arylene group represented by Ar in formula (2), preferably , One or two groups arbitrarily selected from the arylene groups represented by formula (A-1) to formula (A-12).
In general formula (1-a) to general formula (6-a), X ₁ and X ₂ represent the same meaning as in formula (1), and n represents an integer of 2 or more.

Compound A according to the present invention can be produced by referring to a method known per se.
For example, the compound represented by the general formula (1-a) is converted into a compound represented by the general formula (4) and the general formula (5), for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride. And a compound represented by the general formula (6) in the presence of a base.
In addition, the compound represented by the general formula (1-a) may be converted into, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride to the compound represented by the general formula (7) and the general formula (8). And a compound represented by the general formula (9) in the presence of a base (for example, Chem. Rev., 95, 2457 (1995), J. Amer. Chem. Soc. 101, 4992 (1979) can be referred to].

〔式中、Ｘ_１およびＸ_２は式（１）の場合と同じ意味を表し、Ａｒ_１は式（２）においてＡｒで表されるアリーレン基を表し、Ｚ_１およびＺ_２はハロゲン原子を表し、Ｍ_１およびＭ_２は−Ｂ(ＯＨ)_２または−ＳｎＲ_３を表す〕
尚、一般式（４）、一般式（５）および一般式（９）で表される化合物において、Ｚ_１およびＺ_２で表されるハロゲン原子は、好ましくは、塩素原子、臭素原子、ヨウ素原子である。
また、一般式（６）、一般式（７）および一般式（８）で表される化合物において、
Ｍ_１およびＭ_２で表される−ＳｎＲ_３中のアルキル基Ｒは、好ましくは、炭素数１〜４のアルキル基を表す。

[Wherein, X ₁ and X ₂ represent the same meaning as in formula (1), Ar ₁ represents an arylene group represented by Ar in formula (2), and Z ₁ and Z ₂ represent a halogen atom. , M ₁ and M ₂ represent —B (OH) ₂ or —SnR ₃ ]
In the compounds represented by general formula (4), general formula (5) and general formula (9), the halogen atom represented by Z ₁ and Z ₂ is preferably a chlorine atom, a bromine atom or an iodine atom. It is.
In the compounds represented by general formula (6), general formula (7) and general formula (8),
The alkyl group R in —SnR ₃ represented by M ₁ and M ₂ preferably represents an alkyl group having 1 to 4 carbon atoms.

〔式中、Ａｒ_１およびＡｒ_２はそれぞれ独立に、式（２）においてＡｒで表されるアリーレン基を表し、Ｚ_１およびＺ_２はハロゲン原子を表し、Ｍ_１およびＭ_２は−Ｂ（ＯＨ）_２または−ＳｎＲ_３を表す〕
尚、一般式（１０）で表される化合物において、Ｍ_１およびＭ_２で表される−ＳｎＲ_３中のアルキル基Ｒは、好ましくは、炭素数１〜４のアルキル基を表す。
一般式（１１）で表される化合物において、Ｚ_１およびＺ_２で表されるハロゲン原子は、好ましくは、塩素原子、臭素原子、ヨウ素原子である。
The compound represented by the general formula (2-a) is converted into, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a compound represented by the general formula (4) and the general formula (5). It can be produced by reacting the compound represented by the general formula (10) in the presence of a base.
In addition, the compound represented by the general formula (2-a) can be converted into, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride to the compound represented by the general formula (7) and the general formula (8). And a compound represented by the general formula (11) in the presence of a base.

[In the formula, Ar ₁ and Ar ₂ each independently represent an arylene group represented by Ar in Formula (2), Z ₁ and Z ₂ represent a halogen atom, and M ₁ and M ₂ represent —B (OH ] Represents ₂ or -SnR ₃ ]
In the compound represented by the general formula (10), the alkyl group R in —SnR ₃ represented by M ₁ and M ₂ preferably represents an alkyl group having 1 to 4 carbon atoms.
In the compound represented by the general formula (11), the halogen atom represented by Z ₁ and Z ₂ is preferably a chlorine atom, a bromine atom, or an iodine atom.

The compound represented by the general formula (3-a) is a compound represented by the general formula (12), for example, in the presence of a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a base. It can manufacture by making the compound represented by Formula (6) act.
In addition, the compound represented by the general formula (3-a) is added to the compound represented by the general formula (13) in the presence of, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a base. And a compound represented by the general formula (9) can be produced [for example, Chem. Rev., 95, 2457 (1995), J. Amer. Chem. Soc., 101, 4992 (1979 ) Can be referred to].

〔式中、Ｘ_１およびＸ_２は式（１）の場合と同じ意味を表し、Ｚ_１およびＺ_２はハロゲン原子を表し、Ｍ_１およびＭ_２は−Ｂ（ＯＨ）_２または−ＳｎＲ_３を表す〕
尚、一般式（１２）で表される化合物において、Ｚ_１およびＺ_２で表されるハロゲン原子は、好ましくは、塩素原子、臭素原子、ヨウ素原子である。
また、一般式（１３）で表される化合物において、Ｍ_１およびＭ_２で表される−ＳｎＲ_３中のアルキル基Ｒは、好ましくは、炭素数１〜４のアルキル基を表す。
The compound represented by the general formula (4-a) is a compound represented by the general formula (12), for example, in the presence of a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a base. It can manufacture by making the compound represented by Formula (10) act.
In addition, the compound represented by the general formula (4-a) is added to the compound represented by the general formula (13), for example, in the presence of a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a base. It can be produced by reacting the compound represented by the general formula (11).

[Wherein, X ₁ and X ₂ represent the same meaning as in formula (1), Z ₁ and Z ₂ represent a halogen atom, M ₁ and M ₂ represent —B (OH) ₂ or —SnR ₃ To express〕
In the compound represented by the general formula (12), the halogen atom represented by Z ₁ and Z ₂ is preferably a chlorine atom, a bromine atom, or an iodine atom.
In the compound represented by the general formula (13), the alkyl group R in —SnR ₃ represented by M ₁ and M ₂ preferably represents an alkyl group having 1 to 4 carbon atoms.

〔式中、Ｘ_１およびＸ_２は式（１）の場合と同じ意味を表し、Ａｒ_１は式（２）においてＡｒで表されるアリーレン基を表し、Ｚ_１およびＺ_２はハロゲン原子を表し、Ｍ_１およびＭ_２は−Ｂ（ＯＨ）_２または−ＳｎＲ_３を表す〕
尚、一般式（１４）で表される化合物において、Ｚ_１およびＺ_２で表されるハロゲン原子は、好ましくは、塩素原子、臭素原子、ヨウ素原子である。
また、一般式（１５）で表される化合物において、Ｍ_１およびＭ_２で表される−ＳｎＲ_３中のアルキル基Ｒは、好ましくは、炭素数１〜４のアルキル基を表す。
The compound represented by the general formula (5-a) is obtained by, for example, reacting an alkylmagnesium halide with the compound represented by the general formula (14), and then a nickel catalyst [for example, Ni (dppp) Cl ₂ ( , Dppp represents diphenylphosphinopropane)] can be produced (for example, the method described in Macromolecules., 34, 4324 (2001) can be referred to).
In addition, the compound represented by the general formula (5-a) is added to the compound represented by the general formula (14) in the presence of, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a base. Can be produced by reacting the compound represented by the general formula (15) [for example, Chem. Rev., 95, 2457 (1995), J. Amer. Chem. Soc., 101, 4992 (1979 ) Can be referred to].

[Wherein, X ₁ and X ₂ represent the same meaning as in formula (1), Ar ₁ represents an arylene group represented by Ar in formula (2), and Z ₁ and Z ₂ represent a halogen atom. , M ₁ and M ₂ represent —B (OH) ₂ or —SnR ₃ ]
In the compound represented by the general formula (14), the halogen atom represented by Z ₁ and Z ₂ is preferably a chlorine atom, a bromine atom, or an iodine atom.
In the compound represented by the general formula (15), the alkyl group R in —SnR ₃ represented by M ₁ and M ₂ preferably represents an alkyl group having 1 to 4 carbon atoms.

〔式中、Ａｒ_２は式（２）においてＡｒで表されるアリーレン基を表し、Ｚ_１およびＺ_２はハロゲン原子を表し、Ｍ_１およびＭ_２は−Ｂ（ＯＨ）_２または−ＳｎＲ_３を表す〕
尚、一般式（１６）で表される化合物において、Ｍ_１およびＭ_２で表される−ＳｎＲ_３中のアルキル基Ｒは、好ましくは、炭素数１〜４のアルキル基を表す。
また、一般式（１７）で表される化合物において、Ｚ_１およびＺ_２で表されるハロゲン原子は、好ましくは、塩素原子、臭素原子、ヨウ素原子である。 The compound represented by the general formula (6-a) is, for example, a compound represented by the general formula (14) in the presence of, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a base. It can be produced by reacting the compound represented by the general formula (16).
In addition, the compound represented by the general formula (6-a) is added to the compound represented by the general formula (15) in the presence of, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride] and a base. Can be produced by reacting a compound represented by the general formula (17) [for example, Chem. Rev., 95, 2457 (1995), J. Amer. Chem. Soc., 101, 4992 (1979 ) Can be referred to].

[In the formula, Ar ₂ represents an arylene group represented by Ar in Formula (2), Z ₁ and Z ₂ represent a halogen atom, M ₁ and M ₂ represent —B (OH) ₂ or —SnR ₃ To express〕
In the compound represented by the general formula (16), the alkyl group R in —SnR ₃ represented by M ₁ and M ₂ preferably represents an alkyl group having 1 to 4 carbon atoms.
In the compound represented by the general formula (17), the halogen atom represented by Z ₁ and Z ₂ is preferably a chlorine atom, a bromine atom, or an iodine atom.

Specific examples of the compound A according to the present invention include the following compounds, but the present invention is not limited thereto.
In the exemplified compounds, n represents an integer of 2 or more.

The compound A according to the present invention may be produced in a form that forms a solvate with a solvent used in some cases (for example, an aromatic hydrocarbon solvent such as toluene). In addition to the non-solvate of Compound A according to the present invention, such a solvate can also be used. When the compound A according to the present invention is used in an organic transistor, a recrystallization method, a column chromatography method, a purification method such as a sublimation purification method, or a compound having an increased purity by using these methods in combination. Is preferred.

The organic transistor usually has a source electrode, a drain electrode and a gate electrode, a gate insulating layer, and an organic semiconductor layer. In the organic transistor of the present invention, the organic semiconductor layer includes the compound according to the present invention. It contains at least one kind of A.

The form of the organic transistor of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an embodiment of the organic transistor of the present invention.
In the form of this organic transistor, a gate electrode 21 is provided on a substrate 11, a gate insulating layer 31 is laminated on the gate electrode, and a source electrode 61 and a drain electrode formed on the gate electrode at predetermined intervals. 41 is formed, and an organic semiconductor layer 51 is further stacked thereon (bottom gate / bottom contact structure).

In the form of the organic transistor shown in FIG. 2, the gate electrode 22 is provided on the substrate 12, the gate insulating layer 32 is laminated on the gate electrode, and the organic semiconductor layer 52 is laminated thereon. Further, a source electrode 62 and a drain electrode 42 are formed at a predetermined interval thereon (bottom gate / top contact structure).

In the form of the organic transistor shown in FIG. 3, the source electrode 63 and the drain electrode 43 are formed on the substrate 13 at a predetermined interval, and the organic semiconductor layer 53 is laminated thereon, A gate insulating layer 33 is laminated thereon, and a gate electrode 23 is further provided thereon (top gate / bottom contact structure).

In the form of the organic transistor shown in FIG. 4, the organic semiconductor layer 54 is laminated on the substrate 14, and the source electrode 64 and the drain electrode 44 are formed on the substrate 14 at a predetermined interval. A gate insulating layer 34 is laminated thereon, and a gate electrode 24 is further provided thereon (top gate / top contact structure).

In the organic transistor having such a structure, the organic semiconductor layer forms a channel region, and the current flowing between the source electrode and the drain electrode is controlled by the voltage applied to the gate electrode, thereby turning on / off. Operate.

The substrate used in the organic transistor of the present invention is not particularly limited, but generally, glass, quartz, silicon single crystal, polycrystalline silicon, amorphous silicon, a plastic substrate, or the like can be used. Furthermore, a composite substrate in which these are combined can be used, and may have a single-layer structure or a multilayer structure.

Examples of the plastic substrate include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, triacetylcellulose, and cellulose acetate propionate. A substrate is mentioned.
Note that when a conductive substrate, for example, silicon is used for the substrate, the substrate can also serve as the gate electrode.

In the organic transistor of the present invention, materials used for the source electrode, the drain electrode, and the gate electrode are not particularly limited, and any material can be used as long as it is a conductive material.

Examples of the electrode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide (IZO), gold, silver, platinum, copper, indium, aluminum, magnesium, nickel, chromium, iron, tin, Tantalum, palladium, tellurium, iridium, ruthenium, germanium, tungsten, lithium, beryllium, sodium, potassium, calcium, zinc, magnesium / indium alloy, magnesium / copper alloy, magnesium / silver alloy, magnesium / aluminum alloy, chromium / molybdenum alloy Metal / alloys such as aluminum / lithium alloy, aluminum / scandium / lithium alloy, sodium / potassium alloy, fluorine doped zinc oxide, silicon single crystal with improved conductivity, polycrystalline silicon, aluminum Examples include silicon-based materials such as Rufus silicon, and carbon materials such as carbon black, graphite, and glassy carbon. More preferably, indium tin oxide alloy, gold, silver, platinum, copper, indium, aluminum, conductivity Improved silicon-based materials and carbon materials. These can be used in various forms such as bulk, flakes, and fine particles.

In addition, as an electrode material, a conductive polymer whose conductivity has been improved by doping treatment (eg, polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid complex, etc.) Are also preferably used.
These electrode materials may be used alone or in combination.
Among the electrode materials listed above, the source electrode and the drain electrode are preferably those having a small electric resistance at the contact surface with the organic semiconductor layer.

A method for forming each electrode is not particularly limited. For example, a conductive material can be formed using a method such as vapor deposition or sputtering, and patterned into a desired shape by lithograph or etching treatment. it can.
In addition, when an electrode is formed using a conductive polymer or conductive fine particles, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be patterned by an ink jet method. It may be formed by lithography or laser ablation. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste (silver paste, carbon paste, etc.) by a printing method such as relief printing, intaglio printing, planographic printing, and screen printing can also be used.

The film thickness of the source electrode and the drain electrode is not particularly limited, but in general, it is preferably set in the range of several nm to several hundred μm, more preferably 1 nm to 100 μm, and still more preferably 10 nm. ˜20 μm.
The source electrode and the drain electrode are arranged so as to face each other, and the interval (channel length) is generally preferably set in the range of several hundred nm to several mm, more preferably 100 nm to It is 1 mm, More preferably, it is 1 micrometer-500 micrometers.

Further, the surface of the source electrode and the drain electrode is, for example, an aliphatic alkyl thiol compound such as 4,4-dimethylpentanethiol, perfluorohexanethiol, perfluoroheptanethiol, and perfluorooctanethiol, for example, 2,4,6. -It may be modified with an aromatic thiol compound such as trifluorothiophenol, pentafluorothiophenol, 4-trifluoromethylthiophenol.

As a material used for the gate insulating layer, various insulating materials can be used, and an inorganic insulator or an organic polymer compound is preferable.
Inorganic insulators include silicon oxide (SiO ₂ ), silicon nitride, aluminum oxide, aluminum nitride, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate , Lead lanthanum titanate, strontium titanate, barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, trioxide yttrium, and more Preferred are silicon oxide, silicon nitride, aluminum oxide, tantalum oxide, and titanium oxide.

Examples of the method for forming a gate insulating layer made of an inorganic insulator include a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, and atmospheric pressure plasma. Dry processes such as spray coating, spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, air knife, slide hopper, and extrusion Examples thereof include a wet process such as a coating method, various printing methods, and an inkjet method, and can be appropriately selected and applied according to the characteristics of the material to be used. Further, when a silicon-based material is used as the gate electrode and the gate insulating layer is formed before the organic semiconductor is formed, it may be formed by thermal oxidation.

Examples of the organic polymer compound used for the gate insulating layer include polyimide, polyamide, polyester, polyacrylate, a photo-radical polymerization photo-curing resin, a photo-cation polymerization photo-curing resin, or a copolymer containing an acrylonitrile component. Polyvinylphenol, polyvinyl alcohol, polystyrene, novolac resin, polyvinylidene fluoride, cyanoethyl pullulan, and the like can be used. As a method for forming a gate insulating layer using an organic polymer compound, a wet process is preferable.
The insulating material used for the gate insulating layer may be used alone or in combination.

In addition, when using, for example, silicon oxide as an inorganic insulator for the gate insulating layer, the surface of silicon oxide serving as an interface with the organic semiconductor layer is, for example, hexamethyldisilazane, octadecyltrimethoxysilane, octyltrichlorosilane, Octadecyltrichlorosilane, benzyltrichlorosilane, 1-hexylphosphonic acid, 1-octylphosphonic acid, 1-hexadecylphosphonic acid, 3,7,11,15-tetramethyl-1-hexadecylphosphonic acid, etc. It may be processed.
When an organic polymer compound is used for the gate insulating layer and the organic semiconductor layer is formed after forming the gate insulating layer, the organic semiconductor layer is subjected to a rubbing treatment on the gate insulating layer made of the organic polymer compound. May be formed.

The thickness of the gate insulating layer is not particularly limited, but generally it is preferably set in the range of several nm to several tens of μm, more preferably 5 nm to 10 μm, and still more preferably 10 nm to 5 μm. It is.

The organic transistor of the present invention comprises at least one compound A according to the present invention in an organic semiconductor layer, and the compound A according to the present invention may be used alone or in combination. May be used in combination.

In addition, the organic semiconductor layer is composed of the compound A according to the present invention and other carrier transporting compounds (for example, polyacetylene derivatives, polythiophene derivatives, polythienylene vinylene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polypyrrole derivatives, polyaniline derivatives, polyquinoline). Derivatives, perylene derivatives, tetracene derivatives, pentacene derivatives, phthalocyanine derivatives, and the like). In this case, the content of the compound A according to the present invention is preferably 20% by mass or more, and more preferably 50% by mass or more.

Furthermore, the organic semiconductor layer may be formed from the compound A according to the present invention and a polymer compound. Examples of the polymer compound include polyacrylic acid derivatives, polymethacrylic acid derivatives, poly (cyclohexyl methacrylate) derivatives, polyethylene derivatives, polypropylene derivatives, polyisoprene derivatives, polybutadiene derivatives, polyisobutylene derivatives, polymethylpentene derivatives, poly ( Vinylcyclohexane) derivatives, polystyrene derivatives, poly (4-methylstyrene) derivatives, poly (α-methylstyrene) derivatives, poly (α-vinylnaphthalene) derivatives, poly (vinyltoluene) derivatives, poly (chlorotrifluoroethylene) derivatives , Poly (4-vinylbiphenyl) derivatives, poly (2-methyl-1,3-butadiene) derivatives, poly (styrene / acrylonitrile) copolymers, poly (styrene / butadiene) copolymers, polyvinyl chloride And the like, and the like, and the like, and polyethylene derivatives, polyethylene terephthalate derivatives, polybutylene terephthalate derivatives, nylon derivatives, polyester derivatives, polyimide derivatives, polyphenol derivatives, cellulose derivatives, vinylon derivatives, and the like.
These polymer compounds may be used alone or in combination.
When the organic semiconductor layer is formed by using the compound A according to the present invention in combination with the polymer compound, the content of the compound A according to the present invention is preferably 5% by mass or more based on the polymer compound. It is more preferable to prepare so that it may become 20 mass% or more.

The organic transistor of the present invention functions as a p-type (holes function as a carrier) organic transistor or an n-type (electrons function as a carrier) organic transistor, preferably as a p-type organic transistor. It is preferred to use.
The method for forming the organic semiconductor layer is not particularly limited, and a known formation method can be used. Examples of the formation method include vacuum deposition, molecular beam epitaxial growth, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, plasma polymerization, thermal transfer, and laser transfer. Dry process, spray coat method, spin coat method, blade coat method, dip coat method, cast method, roll coat method, bar coat method, die coat method, LB method (Langmuir / Blodget method), various printing methods, ink jet method, etc. Can be mentioned.

When the organic semiconductor layer is formed by a wet process, a solution in which the compound A according to the present invention is dissolved or dispersed in a solvent is used.
Examples of such solvents include alcohol solvents such as water, methanol, ethanol, isopropyl alcohol, and butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; Ether solvents such as ether, dioxane, tetrahydrofuran, anisole, hydrocarbon solvents such as hexane, octane, toluene, xylene, ethylbenzene, cumene, dichloromethane, chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, chlorobenzene, fluorobenzene, dichlorobenzene, Halogenated hydrocarbon solvents such as trichlorobenzene, acetonitrile, propionitrile, methoxyacetonitrile, gluta Examples include nitrile solvents such as dinitrile and benzonitrile, aprotic polar solvents such as dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Can do. These solvents may be used alone or in combination.
The concentration of the compound A according to the present invention in such a solvent is not particularly limited,
In general, it is preferable to adjust to 0.01 to 20% by mass, more preferably about 0.05 to 15% by mass.
The film thickness of the organic semiconductor layer is not particularly limited, but in general, it is preferably set in the range of several nm to several tens of μm, more preferably 1 nm to 10 μm, still more preferably 5 nm to 1 μm.

In the organic transistor of the present invention, the organic semiconductor layer may be subjected to a doping treatment if desired.
In addition, as a dopant, both a donor-type dopant and an acceptor-type dopant can be used, and it is preferable to use an acceptor-type dopant.

As the donor dopant, any compound having a function of donating electrons to the organic compound of the organic semiconductor layer can be preferably used. As a donor dopant, for example,
Alkali metals such as Li, Na, K, Rb, Cs, alkaline earth metals such as Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Rare earth metals such as Yb, ammonium ions, R ₄ P ⁺ (R represents an alkyl group), R ₄ As ⁺ (R represents an alkyl group), R ₃ S ⁺ (R represents an alkyl group), acetylcholine, etc. Is mentioned.

As the acceptor dopant, any compound having a function of removing electrons from the organic compound of the organic semiconductor layer can be preferably used.
Examples of the acceptor dopant include Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ ,
Halogen compounds such as IBr and IF, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ ,
Lewis acids such as BBr ₃ and SO ₃ , HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ ,
Protic acids such as FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, organic acids such as acetic acid, formic acid, amino acids, FeCl ₃ , FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ ,
NbCl ₅ , TaCl ₅ , MoCl ₅ , WF ₅ , WCl ₆ , UF ₆ , LnCl ₃ (Ln = La,
Lanthanoids such as Ce, Nd, Pr and transition metal compounds such as Y), Cl ⁻ , Br ⁻ , I ⁻ ,
Examples thereof include electrolyte anions such as ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₅ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ and sulfonate anions.
As a doping method, a method of introducing a dopant after forming an organic semiconductor layer, or a method of introducing a dopant at the time of forming the organic semiconductor layer can be applied.

Moreover, the organic transistor of this invention can also provide a gas barrier layer in the whole or part of the outer peripheral surface of an organic transistor in order to reduce the influence of oxygen, moisture, etc. in the atmosphere. Examples of the material for forming the gas barrier layer include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl chloride, and polyvinylidene chloride. Furthermore, the inorganic insulator mentioned as a material used for a gate insulating layer can also be used for formation of a gas barrier layer.

The organic transistor of the present invention can be used for, for example, a liquid crystal display element, an organic electroluminescent element, electronic paper, various sensors, RFIDs (radio frequency identification cards), and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

Example 1
A thermal oxide film (SiO ₂ ) having a thickness of 200 nm was formed on a silicon substrate having a resistivity of 0.02 Ω · cm as a gate electrode. Here, the silicon substrate itself becomes the gate electrode, and the SiO ₂ layer formed on the surface of the silicon substrate becomes the gate insulating layer. When the silicon substrate was heated to 80 ° C. and a chlorobenzene solution (concentration: 0.4 mass%) of the compound of Exemplified Compound No. 11 was applied on the silicon substrate, the chlorobenzene evaporated to give an exemplary compound having a thickness of 80 nm. An organic semiconductor layer made of the compound of No. 11 was formed. Further, a source electrode and a drain electrode were formed thereon by vapor-depositing gold using a mask. The source electrode and drain electrode had a thickness of 80 nm, a channel width of 2 mm, and a channel length of 50 μm.
The organic transistor manufactured as described above exhibited characteristics as a p-type transistor element. The charge mobility was determined from the saturation region of the current-voltage (IV) characteristics of the organic transistor.
Further, the drain current value was measured when the drain bias was −50 V and the gate bias was −50 V and 0 V, and the current on / off ratio was obtained.
Furthermore, after storing the produced organic transistor element in the atmosphere at 25 ° C. for one month, the charge mobility and the on / off ratio of the current were measured again. The measurement results are shown in Table 1.

(Examples 2 to 8)
In Example 1, instead of using the compound of Exemplified Compound No. 11 in forming the organic semiconductor layer, the compound of Exemplified Compound No. 25 (Example 2), the Compound of Exemplified Compound No. 33 (Example 3), and the Exemplified Compound Compound No. 53 (Mn = 13400) (Example 4), Compound No. 65 (Mn = 15800) (Example 5), Compound No. 67 (Mn = 10800) (Example 6), Example The organic transistor was formed by the method described in Example 1 except that the compound of Compound No. 83 (Mn = 16400) (Example 7) and the compound of Example Compound No. 93 (Mn = 17000) (Example 8) were used. Produced.
Further, the characteristics of the organic transistor were examined by the method described in Example 1, and the results are shown in Table 1.

(Comparative Example 1)
In Example 1, the organic semiconductor layer was formed in the same manner as in Example 1 except that the polythiophene [the following comparative compound (Mn = 17000)] described in Patent Document 1 was used instead of the compound of Exemplified Compound No. 11. An organic transistor was produced by the method described in 1.
Further, the characteristics of the organic transistor were examined by the method described in Example 1, and the results are shown in Table 1.

Example 9
A thermal oxide film (SiO ₂ ) having a thickness of 200 nm was formed on a silicon substrate having a resistivity of 0.02 Ω · cm as a gate electrode. Here, the silicon substrate itself becomes the gate electrode, and the SiO ₂ layer formed on the surface of the silicon substrate becomes the gate insulating layer. On top of this, under vacuum (5 × 10 ⁻⁴ Pa), the compound of Exemplary Compound No. 3 was deposited to a thickness of 40 nm at a deposition rate of 0.03 nm / sec to form an organic semiconductor layer. Further, a source electrode and a drain electrode were formed thereon by vapor-depositing gold using a mask. The source electrode and drain electrode had a thickness of 80 nm, a channel width of 2 mm, and a channel length of 50 μm.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 3.5 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 2.7. × 10 ⁷

(Example 10)
In Example 9, when the organic semiconductor layer was formed, an organic transistor was produced by the method described in Example 9 except that the compound of exemplary compound number 12 was used instead of the compound of exemplary compound number 3. .
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 2.8 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 3.2. × 10 ⁷

第１表より、本発明の有機トランジスタは、高い電荷移動度、大きな電流オン／オフ比を有し、有機トランジスタとして優れた特性を有しており、さらに経時変化が抑制された、安定性に優れた有機トランジスタであることが明らかである。

From Table 1, the organic transistor of the present invention has a high charge mobility, a large current on / off ratio, has excellent characteristics as an organic transistor, and further has a stable change with time. It is clear that it is an excellent organic transistor.

  The organic transistor of the present invention has high charge mobility, a large current on / off ratio, and excellent storage stability. The liquid crystal display element, organic electroluminescent element, electronic paper, various sensors, RFIDs (radio frequency identification cards).

11: Substrate 21: Gate electrode 31: Gate insulating layer 41: Drain electrode 51: Organic semiconductor layer 61: Source electrode

12: Substrate 22: Gate electrode 32: Gate insulating layer 42: Drain electrode 52: Organic semiconductor layer 62: Source electrode

13: Substrate 23: Gate electrode 33: Gate insulating layer 43: Drain electrode 53: Organic semiconductor layer 63: Source electrode

14: Substrate 24: Gate electrode 34: Gate insulating layer 44: Drain electrode 54: Organic semiconductor layer 64: Source electrode

Claims (1)

In the organic transistor having an organic semiconductor layer, the organic semiconductor layer contains at least two structural units represented by the formula (1) in one repeating unit,

Wherein X ₁ and X ₂ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group Or a substituted or unsubstituted aryl group, and two or more structural units may be the same group or different groups)
And containing at least one structural unit represented by formula (2),
-Ar- (2)
(In the formula, Ar represents a substituted or unsubstituted arylene group, and when there are two or more structural units, they may be the same group or different groups)
An organic transistor comprising at least one oligomer or polymer in which the number of repeating units composed of structural units represented by formulas (1) and (2) is 1 to 10,000.

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