JP5843304B2 - Organic transistor - Google Patents

Description

The present invention relates to an organic transistor containing a thiophene compound having a specific structure.

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 order to improve these storage stability, an organic transistor using a [1] benzothieno [3,2-b] [1] benzothiophene derivative as an organic semiconductor layer has been proposed.
For example, an organic transistor using 2,7-diphenyl [1] benzothieno [3,2-b] [1] benzothiophene as an organic semiconductor layer has been proposed (Non-Patent Document 4).
An organic transistor using 2,7-dialkyl [1] benzothieno [3,2-b] [1] benzothiophene for an organic semiconductor layer has been proposed (Non-patent Document 5).
For example, an organic transistor using 2,7-dialkoxyalkyl [1] benzothieno [3,2-b] [1] benzothiophene as an organic semiconductor layer has been proposed (Patent Document 1). Further, an organic transistor using a compound in which a benzene ring is condensed to [1] benzothieno [3,2-b] [1] benzothiophene is proposed for an organic semiconductor layer (Patent Documents 2 and 3).
These various 2,7-disubstituted [1] benzothieno [3,2-b] [1] benzothiophene derivatives and [1] benzothieno [3,2-b] [1] benzones fused with a benzene ring An organic transistor containing a thiophene derivative in an organic semiconductor layer has good storage stability, high charge mobility, and good performance, but at present, the development of a further improved organic transistor for practical application Is required.

JP 2009-267132 A JP 2010-34450 A Republished WO2008 / 050726

Appl.Phys.Lett., 63,1372 (1993) Appl.Phys.Lett., 72,1854 (1998) Science, 268,270 (1995) J. Amer. Chem. Soc., 128, 12604 (2006) J. Amer. Chem. Soc., 129, 15732 (2007)

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, a low threshold voltage, and excellent storage stability.

As a result of intensive studies to solve the above problems, the present inventor contains at least one compound selected from the compounds represented by the general formulas (1) to (3) in the organic semiconductor layer. The organic transistor was found to have high charge mobility, a large current on / off ratio, a low threshold voltage, and excellent storage stability, and the present invention was completed.
That is, the present invention
The organic transistor having an organic semiconductor layer is an organic transistor containing at least one compound selected from compounds represented by the general formulas (1) to (3) in the organic semiconductor layer.

〔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、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表す（但し、Ｘ_１およびＸ_２が同時に水素原子、あるいは置換または未置換のアリール基を表すことはない）〕

[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. Represents a linear, branched or cyclic alkoxyalkoxy group or a substituted or unsubstituted aryl group (provided that X ₁ and X ₂ do not represent a hydrogen atom or a substituted or unsubstituted aryl group at the same time)]

〔式中、Ｘ_３およびＸ_４はそれぞれ独立に、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、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表す〕

[Wherein, X ₃ and X ₄ each independently represent 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 linear chain. Represents a branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group.

〔式中、Ｘ_５〜Ｘ_８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、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表し（但し、Ｘ_５〜Ｘ_８の少なくとも１つは、直鎖、分岐または環状のアルコキシアルキル基、あるいは直鎖、分岐または環状のアルコキシアルコキシ基を表す）、ａは０または１を表す〕

[Wherein, X _{5 to} X ₈ 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. Represents a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group (provided that at least one of X _{5 to} X ₈ represents a linear, branched or cyclic alkoxyalkyl group, or a linear Represents a branched or cyclic alkoxyalkoxy group), a represents 0 or 1]

According to the present invention, it is possible to provide an organic transistor having high charge mobility, a large current on / off ratio, a low threshold voltage, 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.

Hereinafter, the present invention will be described in detail.
The organic transistor of the present invention is an organic transistor comprising at least one compound selected from compounds represented by the general formulas (1) to (3) in the organic semiconductor layer.

〔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、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表す（但し、Ｘ_１およびＸ_２が同時に水素原子、あるいは置換または未置換のアリール基を表すことはない）〕

[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. Represents a linear, branched or cyclic alkoxyalkoxy group or a substituted or unsubstituted aryl group (provided that X ₁ and X ₂ do not represent a hydrogen atom or a substituted or unsubstituted aryl group at the same time)]

〔式中、Ｘ_３およびＸ_４はそれぞれ独立に、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、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表す〕

[Wherein, X ₃ and X ₄ each independently represent 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 linear chain. Represents a branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group.

〔式中、Ｘ_５〜Ｘ_８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、直鎖、分岐または環状のアルコキシアルコキシ基、あるいは置換または未置換のアリール基を表し（但し、Ｘ_５〜Ｘ_８の少なくとも１つは、直鎖、分岐または環状のアルコキシアルキル基、あるいは直鎖、分岐または環状のアルコキシアルコキシ基を表す）、ａは０または１を表す〕

[Wherein, X _{5 to} X ₈ 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. Represents a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group (provided that at least one of X _{5 to} X ₈ represents a linear, branched or cyclic alkoxyalkyl group, or a linear Represents a branched or cyclic alkoxyalkoxy group), a represents 0 or 1]

[Compound of general formula (1)]
In the compound represented by the general 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, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group.
However, X ₁ and X ₂ do not simultaneously represent a hydrogen atom 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 compound represented by the general 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. Linear, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or 4 to 20 carbon atoms Represents a substituted or unsubstituted aryl group.

In the compound represented by the general formula (1), X ₁ and X ₂ are more preferably a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, or a C _{1 to} 16 carbon atom. A linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group having 2 to 16 carbon atoms, or a linear, branched or cyclic alkoxyalkoxy group having 2 to 16 carbon atoms is represented.

Specific examples of X ₁ and X ₂ in the general formula (1) include, for example, a hydrogen atom; for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and iodine; for example, a methyl group, an ethyl group, and 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-methyl Heptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl Ru-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, 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, a linear, branched or cyclic alkyl group such as a cyclooctyl group;
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, methoxymethoxy group, ethoxymexi group, n-butoxymethoxy group, n-pentyloxymethoxy group, n-hexyloxymethoxy group, (2-ethylbutoxy) methoxy group, n-heptyloxymethoxy group, n-octyloxy Methoxy group, n-decyloxymethoxy group, n-dodecyloxymethoxy group, 1-methoxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 2-isopropoxyethoxy group, 2-n-butoxyethoxy group, 2-n-pentyloxyethoxy group, 2-n-hexyloxyethoxy group, 2- (2′-ethylbutyloxy) ethoxy group, 2-n-heptyloxyethoxy group, 2- n-octyloxyethoxy group, 2- (2′-ethylhexyloxy) ethoxy group, -N-decyloxyethoxy group, 2-n-dodecyloxyethoxy group, 2-n-tetradecyloxyethoxy group, 2-cyclohexyloxyethoxy group, 2-methoxypropoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group Group, 3-n-propoxypropoxy group, 3-isopropoxypropoxy group, 3-n-butoxypropoxy group, 3-n-pentyloxypropoxy group, 3-n-hexyloxypropoxy group, 3- (2′-ethyl) Butoxy) propoxy, 3-n-octyloxypropoxy, 3- (2′-ethylhexyloxy) propoxy, 3-n-decyloxypropoxy, 3-n-dodecyloxypropoxy, 3-n-tetradecyl Oxypropoxy group, 3-cyclohexyloxypropoxy group, 2-methoxy Toxyl group, 3-methoxybutoxy group, 4-methoxybutoxy group, 4-ethoxybutoxy group, 4-n-propoxybutoxy group, 4-isopropoxybutoxy group, 4-n-butoxybutoxy group, 4-n-hexyloxy Butoxy group, 4-n-octyloxybutoxy group, 4-n-decyloxybutoxy group, 4-n-dodecyloxybutoxy group, 5-methoxypentyloxy group, 5-ethoxypentyloxy group, 5-n-propoxypentyl Oxy group, 5-n-pentyloxypentyloxy group, 6-methoxyhexyloxy group, 6-ethoxyhexyloxy group, 6-isopropoxyhexyloxy group, 6-n-butoxyhexyloxy group, 6-n-hexyloxy Hexyloxy group, 6-n-decyloxyhexyloxy group, 4-methoxy Hexyloxy group, 7-methoxyheptyloxy group, 7-ethoxyheptyloxy group, 7-isopropoxyheptyloxy group, 8-methoxyoctyloxy group, 8-ethoxyoctyloxy group, 9-methoxynonyloxy group, 9-ethoxy Nonyloxy group, 10-methoxydecyloxy group, 10-ethoxydecyloxy group, 10-n-butoxydecyloxy group, 11-methoxyundecyloxy group, 11-ethoxyundecyloxy group, 12-methoxydodecyloxy group, Linear, branched or cyclic alkoxyalkoxy groups such as 12-ethoxydodecyloxy group, 12-isopropoxide decyloxy group, 14-methoxytetradecyloxy group, tetrahydrofurfuryloxy 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-2-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) ) Substitution of 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. Or an unsubstituted aryl group can be mentioned.

[Compound of general formula (2)]
In the compound represented by the general formula (2), X ₃ and X ₄ each independently represent a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or A cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group is represented.

In the compound represented by the general formula (2), X ₃ and X ₄ are more preferably a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear chain having 1 to 20 carbon atoms. A branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or a substitution having 4 to 20 carbon atoms Or an unsubstituted aryl group is represented.

In the compound represented by the general formula (2), X ₃ and X ₄ are more preferably a fluorine atom, a straight chain having 1 to 16 carbon atoms, a branched or cyclic alkyl group, and a straight chain having 1 to 16 carbon atoms. A branched or cyclic alkoxy group, a linear or branched alkoxyalkyl group having 2 to 16 carbon atoms, a linear or branched alkoxycyclic group having 2 to 16 carbon atoms, or a substitution having 4 to 16 carbon atoms Or an unsubstituted aryl group is represented.

In the compound represented by the general formula (2), X ₃ and X ₄ are particularly preferably a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or a straight chain having 2 to 12 carbon atoms. Represents a chain, branched or cyclic alkoxyalkyl group.

In the compound represented by the general formula (2), a halogen atom represented by X ₃ and X ₄ , a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic group Specific examples of the alkoxyalkyl group, the linear, branched or cyclic alkoxyalkoxy group, or the substituted or unsubstituted aryl group include, for example, X ₁ and X ₂ in the compound represented by the general formula (1) Halogen atoms, linear, branched or cyclic alkyl groups, linear, branched or cyclic alkoxy groups, linear, branched or cyclic alkoxyalkyl groups, linear, branched or cyclic alkoxyalkoxy groups, substituted or non-substituted A substituted aryl group can be mentioned.

[Compound of general formula (3)]
In the compound represented by the general formula (3), X _{5 to} X ₈ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a linear chain. Represents a branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group.
Provided that at least one of X ₅ to X ₈ represents a straight-chain, branched or cyclic alkoxyalkyl group or a linear, branched or cyclic alkoxyalkoxy group.

In the compound represented by the general formula (3), more preferably, X _{5 to} X ₈ are 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. Linear, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or 4 to 20 carbon atoms Represents a substituted or unsubstituted aryl group.

In the compound represented by the general formula (3), X ₅ or / and X ₇ is more preferably a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, or a linear chain having 2 to 20 carbon atoms. Represents a branched or cyclic alkoxyalkoxy group.

In the compound represented by the general formula (3), a represents 0 or 1.
In the compound represented by the general formula (3), when a represents 0, X ₅ or / and X ₇ is preferably a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, or carbon. A linear, branched or cyclic alkoxyalkoxy group of 2 to 20 is represented.
In the compound represented by the general formula (3), when a represents 0, X ₇ and X ₈ are more preferably a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents -20 linear, branched or cyclic alkoxyalkoxy groups.

In the compound represented by the general formula (3), when a represents 1, more preferably X ₅ and X ₇ are linear, branched or cyclic alkoxyalkyl groups having 2 to 20 carbon atoms, or 2 carbon atoms. linear to 20, represents a branched or cyclic alkoxyalkoxy group, X ₆ and X ₈ represents a hydrogen atom.

In the compound represented by the general formula (3), a halogen atom represented by X _{5 to} X ₈ , a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic group Specific examples of the alkoxyalkyl group, the linear, branched or cyclic alkoxyalkoxy group, or the substituted or unsubstituted aryl group include, for example, X ₁ and X ₂ in the compound represented by the general formula (1) Halogen atoms, linear, branched or cyclic alkyl groups, linear, branched or cyclic alkoxy groups, linear, branched or cyclic alkoxyalkyl groups, linear, branched or cyclic alkoxyalkoxy groups, substituted or non-substituted A substituted aryl group can be mentioned.

The organic transistor of the present invention is characterized in that the organic semiconductor layer contains at least one compound selected from compounds represented by the general formulas (1) to (3). As a result, it is possible to provide an organic transistor that has a high charge mobility, a large current on / off ratio, a low threshold voltage, and excellent storage stability, which has not been conventionally obtained.

Specific examples of the compounds represented by the general formulas (1) to (3) according to the present invention include the following compounds, but the present invention is not limited thereto.

[Method for producing compound]
The compound represented by the general formula (1) according to the present invention, for example, after reacting the compound represented by the general formula (4) or the general formula (5) with an acid (for example, trifluoromethanesulfonic acid), The resulting compound can be produced by reacting with a base (eg, pyridine).

〔式中、Ｘ_１およびＸ_２は一般式（１）の場合と同じ意味を表し、Ｒ_１およびＲ_２はアルキル基を表す〕

また、一般式（２）で表される化合物は、例えば、一般式（６）または一般式（７）で表される化合物と酸（例えば、トリフルオロメタンスルフォン酸）を作用させた後、生成する化合物を塩基（例えば、ピリジン）と作用させて製造することができる。

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

In addition, the compound represented by the general formula (2) is produced, for example, after the compound represented by the general formula (6) or the general formula (7) and an acid (for example, trifluoromethanesulfonic acid) are allowed to act. A compound can be produced by reacting with a base (eg, pyridine).

〔式中、Ｘ_３およびＸ_４は一般式（２）の場合と同じ意味を表し、Ｒ_３およびＲ_４はアルキル基を表す〕

また、一般式（３）で表される化合物は、例えば、一般式（８）または一般式（９）で表される化合物と酸（例えば、トリフルオロメタンスルフォン酸）を作用させた後、生成する化合物を塩基（例えば、ピリジン）と作用させて製造することができる。

[Wherein, X ₃ and X ₄ represent the same meaning as in the general formula (2), and R ₃ and R ₄ represent an alkyl group]

In addition, the compound represented by the general formula (3) is produced, for example, after the compound represented by the general formula (8) or the general formula (9) and an acid (for example, trifluoromethanesulfonic acid) are allowed to act. A compound can be produced by reacting with a base (eg, pyridine).

〔式中、Ｘ_５〜Ｘ_８およびａは一般式（３）の場合と同じ意味を表し、Ｒ_５およびＲ_６はアルキル基を表す〕

一般式（４）〜一般式（９）において、Ｒ_１〜Ｒ_６はアルキル基を表し、好ましくは、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、シクロペンチル基、シクロヘキシル基、ｎ−オクチル基、ｎ−デシル基などの炭素数１〜１０の直鎖、分岐または環状のアルキル基を表し、より好ましくは、メチル基を表す。

[Wherein, X _{5 to} X ₈ and a represent the same meaning as in the general formula (3), and R ₅ and R ₆ represent an alkyl group]

In General Formula (4) to General Formula (9), R _{1 to} R ₆ each represents an alkyl group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert group. Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, such as a butyl group, an n-pentyl group, a cyclopentyl group, a cyclohexyl group, an n-octyl group or an n-decyl group, more preferably a methyl group Represents.

The compound represented by the general formula (4) is, for example, a palladium catalyst [for example, a compound represented by the general formula (10) and a compound represented by the general formula (11) as a catalyst. Bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon] and, if necessary, can be produced by acting in the presence of a base [for example, Chem . Rev. 95, 2457 (1995), Chem. Rev. , 102, 1359 (2002), Chem. Rev. 107, 133 (2007), Tetrahedron, 54, 263 (1998) can be referred to].

〔式中、Ｘ_１およびＸ_２は一般式（１）と同じ意味を表し、Ｒ_１は一般式（４）と同じ意味を表し、Ｍ_１はアルカリ金属、または金属含有基を表し、Ｚ_１はハロゲン原子または−ＯＳＯ_２−Ｒ基を表す〕

同様に、一般式（５）で表される化合物は、例えば、一般式（１２）で表される化合物と、一般式（１３）で表される化合物を、触媒として、例えば、パラジウム触媒［例えば、ビス（トリフェニルフォスフィン）パラジウムジクロライド、テトラキス（トリフェニルフォスフィン）パラジウム、酢酸パラジウム、パラジウム／炭素］、および必要に応じて塩基の存在下で作用させることにより製造することができる。

[Wherein, X ₁ and X ₂ represent the same meaning as in general formula (1), R ₁ represents the same meaning as in general formula (4), M ₁ represents an alkali metal or a metal-containing group, and Z ₁ Represents a halogen atom or —OSO ₂ —R group]

Similarly, the compound represented by the general formula (5) is, for example, a palladium catalyst [for example, a compound represented by the general formula (12) and a compound represented by the general formula (13) as a catalyst. , Bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon], and if necessary, in the presence of a base.

〔式中、Ｘ_１およびＸ_２は一般式（１）と同じ意味を表し、Ｒ_２は一般式（５）と同じ意味を表し、Ｍ_２はアルカリ金属、または金属含有基を表し、Ｚ_２はハロゲン原子または−ＯＳＯ_２−Ｒ基を表す〕

また、一般式（６）で表される化合物は、例えば、一般式（１４）で表される化合物と、一般式（１５）で表される化合物を、触媒として、例えば、パラジウム触媒［例えば、ビス（トリフェニルフォスフィン）パラジウムジクロライド、テトラキス（トリフェニルフォスフィン）パラジウム、酢酸パラジウム、パラジウム／炭素］、および必要に応じて塩基の存在下で作用させることにより製造することができる。

[Wherein, X ₁ and X ₂ represent the same meaning as in general formula (1), R ₂ represents the same meaning as in general formula (5), M ₂ represents an alkali metal or a metal-containing group, Z ₂ Represents a halogen atom or —OSO ₂ —R group]

The compound represented by the general formula (6) is, for example, a palladium catalyst [for example, a compound represented by the general formula (14) and a compound represented by the general formula (15) as a catalyst. It can be produced by acting in the presence of bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon] and, if necessary, a base.

〔式中、Ｘ_３およびＸ_４は一般式（２）と同じ意味を表し、Ｒ_３は一般式（６）と同じ意味を表し、Ｍ_３はアルカリ金属、または金属含有基を表し、Ｚ_３はハロゲン原子または−ＯＳＯ_２−Ｒ基を表す〕

同様に、一般式（７）で表される化合物は、例えば、一般式（１６）で表される化合物と、一般式（１７）で表される化合物を、触媒として、例えば、パラジウム触媒［例えば、ビス（トリフェニルフォスフィン）パラジウムジクロライド、テトラキス（トリフェニルフォスフィン）パラジウム、酢酸パラジウム、パラジウム／炭素］、および必要に応じて塩基の存在下で作用させることにより製造することができる。

[Wherein, X ₃ and X ₄ represent the same meaning as in general formula (2), R ₃ represents the same meaning as in general formula (6), M ₃ represents an alkali metal or a metal-containing group, and Z ₃ Represents a halogen atom or —OSO ₂ —R group]

Similarly, the compound represented by the general formula (7) is, for example, a palladium catalyst [for example, a compound represented by the general formula (16) and a compound represented by the general formula (17) as a catalyst. , Bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon], and if necessary, in the presence of a base.

〔式中、Ｘ_３およびＸ_４は一般式（２）と同じ意味を表し、Ｒ_４は一般式（７）と同じ意味を表し、Ｍ_４はアルカリ金属、または金属含有基を表し、Ｚ_４はハロゲン原子または−ＯＳＯ_２−Ｒ基を表す〕

また、一般式（８）で表される化合物は、例えば、一般式（１８）で表される化合物と、一般式（１９）で表される化合物を、触媒として、例えば、パラジウム触媒［例えば、ビス（トリフェニルフォスフィン）パラジウムジクロライド、テトラキス（トリフェニルフォスフィン）パラジウム、酢酸パラジウム、パラジウム／炭素］、および必要に応じて塩基の存在下で作用させることにより製造することができる。

[Wherein, X ₃ and X ₄ represent the same meaning as in general formula (2), R ₄ represents the same meaning as in general formula (7), M ₄ represents an alkali metal or a metal-containing group, and Z ₄ Represents a halogen atom or —OSO ₂ —R group]

The compound represented by the general formula (8) is, for example, a palladium catalyst [for example, a compound represented by the general formula (18) and a compound represented by the general formula (19) as a catalyst. It can be produced by acting in the presence of bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon] and, if necessary, a base.

〔式中、Ｘ_５〜Ｘ_８およびａは一般式（３）と同じ意味を表し、Ｒ_５は一般式（８）と同じ意味を表し、Ｍ_５はアルカリ金属、または金属含有基を表し、Ｚ_５はハロゲン原子または−ＯＳＯ_２−Ｒ基を表す〕

[Wherein, X _{5 to} X ₈ and a represent the same meaning as in general formula (3), R ₅ represents the same meaning as in general formula (8), M ₅ represents an alkali metal or a metal-containing group, Z ₅ represents a halogen atom or —OSO ₂ —R group]

Similarly, the compound represented by the general formula (9) is, for example, a palladium catalyst [for example, a compound represented by the general formula (20) and a compound represented by the general formula (21) as a catalyst. , Bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon], and if necessary, in the presence of a base.

〔式中、Ｘ_５〜Ｘ_８およびａは一般式（３）と同じ意味を表し、Ｒ_６は一般式（９）と同じ意味を表し、Ｍ_６はアルカリ金属、または金属含有基を表し、Ｚ_６はハロゲン原子または−ＯＳＯ_２−Ｒ基を表す〕

一般式（１０）、一般式（１３）、一般式（１４）、一般式（１７）、一般式（１８）および一般式（２１）において、Ｚ_１〜Ｚ_６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、ヨウ素原子を表し、より好ましくは、臭素原子、ヨウ素原子を表す。

一般式（１０）、一般式（１３）、一般式（１４）、一般式（１７）、一般式（１８）および一般式（２１）において、Ｚ_１〜Ｚ_６で表される−ＯＳＯ_２−Ｒ基において、Ｒは置換または未置換のアリール基、あるいはハロゲン原子で置換されていてもよい直鎖、分岐または環状のアルキル基を表し、より好ましくは、炭素数６〜１０の置換または未置換のアリール基、あるいはハロゲン原子で置換されていてもよい炭素数１〜１０の直鎖、分岐または環状のアルキル基を表し、さらに好ましくは、ハロゲン原子で置換されていてもよい炭素数１〜８の直鎖、分岐または環状のアルキル基を表す。

[Wherein, X _{5 to} X ₈ and a represent the same meaning as in general formula (3), R ₆ represents the same meaning as in general formula (9), M ₆ represents an alkali metal or a metal-containing group, Z ₆ represents a halogen atom or —OSO ₂ —R group]

In general formula (10), general formula (13), general formula (14), general formula (17), general formula (18) and general formula (21), the halogen atom represented by Z _{1 to} Z ₆ is Preferably, a chlorine atom, a bromine atom, and an iodine atom are represented, More preferably, a bromine atom and an iodine atom are represented.

In General Formula (10), General Formula (13), General Formula (14), General Formula (17), General Formula (18), and General Formula (21), —OSO ₂ — represented by Z _{1 to} Z ₆ In the R group, R represents a substituted or unsubstituted aryl group or a linear, branched or cyclic alkyl group which may be substituted with a halogen atom, and more preferably a substituted or unsubstituted group having 6 to 10 carbon atoms. Or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and more preferably 1 to 8 carbon atoms which may be substituted with a halogen atom Represents a linear, branched or cyclic alkyl group.

As specific examples of the substituted or unsubstituted aryl group represented by R of -OSO 2 _-R group, and examples thereof include a phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group and.
In addition, specific examples of the linear, branched or cyclic alkyl group which may be substituted with the halogen atom represented by R of the —OSO ₂ —R group include, for example, a methyl group, an ethyl group, and an n-propyl group. Alkyl groups such as isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, n-octyl group, n-decyl group, trifluoromethyl group, chlorodifluoromethyl And alkyl groups substituted with halogen atoms such as a group, a dichlorofluoromethyl group, a pentafluoroethyl group, and an n-nonafluorobutyl group.
The —OSO ₂ —R group represented by Z _{1 to} Z ₆ is more preferably a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group.

In general formula (11), the general formula (12), the general formula (15), the general formula (16), in the general formula (19) and the general formula _(20), the alkali metal represented by M 1 ~M ₆ Preferably represents Li, Na, K.
In the general formula (11), the general formula (12), the general formula (15), the general formula (16), the general formula (19), and the general formula (20), the metal-containing group represented by M _{1 to} M ₆ is Preferably, boron metal-containing group, tin metal-containing group, magnesium metal-containing group, zinc metal-containing group, manganese metal-containing group, zirconium metal-containing group, indium metal-containing group, germanium metal-containing group, lead metal-containing group, bismuth It represents a metal-containing group or a copper metal-containing group, and more preferably represents a boron metal-containing group, a tin metal-containing group, a magnesium metal-containing group, or a zinc metal-containing group.

The boron metal-containing group is preferably a group represented by the general formula (M-1).
_{-B (OR 0) (OR 00} ) (M-1)
(In the formula, R ₀ and R ₀₀ represent a hydrogen atom or an alkyl group, and R ₀ and R ₀₀ may be bonded to each other to form a cyclic alkylene group or an arylene group)
In General Formula (M-1), R ₀ and R ₀₀ each represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. When R ₀ and R ₀₀ are bonded to each other to represent a cyclic alkylene group, it preferably represents a cyclic alkylene group having 2 to 10 carbon atoms. In addition, when R ₀ and R ₀₀ are bonded to each other to represent an arylene group, it preferably represents a 1,2-phenylene group having 6 to 10 carbon atoms which may be substituted with an alkyl group.

The tin metal-containing group is preferably a group represented by the general formula (M-2).
_{-Sn (R 000) 3 (M} -2)
(In the formula, R ₀₀₀ represents an alkyl group)
In General Formula (M-2), _R000 represents an alkyl group, and preferably represents an alkyl group having 1 to 8 carbon atoms.

The magnesium metal-containing group is preferably a group represented by the general formula (M-3).
-MgZ ₀ (M-3)
(In the formula, Z ₀ represents a halogen atom)
In General Formula (M-3), Z ₀ represents a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.

The zinc metal-containing group is preferably a group represented by the general formula (M-4).
-ZnZ ₀₀ (M-4)
(In the formula, Z ₀₀ represents a halogen atom)
In General Formula (M-4), Z ₀₀ represents a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.

The compounds represented by the general formula (1) to the general formula (3) according to the present invention are produced in a form in which a solvation with a solvent (for example, an aromatic hydrocarbon solvent such as toluene) used in some cases is formed. In the organic transistor of the present invention, such solvates as well as non-solvates of the compounds represented by the general formulas (1) to (3) should be used. Can do.
When the compounds represented by the general formula (1) to the general formula (3) are used in an organic transistor, a recrystallization method, a column chromatography method, a purification method such as a sublimation purification method, or a combination of these methods. It is preferable to use a compound with increased purity.

[Organic transistor]
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 has the general formula (1). -Containing at least 1 type of compound represented by General formula (3).
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.

As electrode materials, for example, indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide (IZO), molybdenum oxide, gold, silver, platinum, copper, indium, aluminum, magnesium, nickel, chromium, iron , Tin, tantalum, palladium, tellurium, iridium, ruthenium, germanium, tungsten, molybdenum, lithium, beryllium, sodium, potassium, calcium, zinc, magnesium / indium alloy, magnesium / copper alloy, magnesium / silver alloy, magnesium / aluminum alloy , Chromium / molybdenum alloy, aluminum / lithium alloy, aluminum / scandium / lithium alloy, sodium / potassium alloy and other metals and alloys, fluorine-doped zinc oxide, silicon with improved conductivity Examples thereof include silicon-based materials such as single crystal, polycrystalline silicon, and amorphous silicon, and carbon materials such as carbon black, graphite, and glassy carbon. More preferably, indium tin oxide alloy, gold, silver, platinum, copper, Indium, aluminum, silicon materials with improved conductivity, 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.
In addition, these electrode materials may be used individually by 1 type, or may be used together.
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 a thermal oxidation method.

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.
In addition, 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 contains at least one compound represented by the general formula (1) to the general formula (3) in the organic semiconductor layer, and is represented by the general formula (1) to the general formula (3). The compound represented by may be used individually by 1 type, and may use multiple types together.
Further, for example, at least one compound represented by the general formula (1) may be used in combination with at least one compound represented by the general formula (2) or the general formula (3).

Further, the organic semiconductor layer includes at least one compound represented by the general formula (1) to the general formula (3) and another carrier transporting compound (for example, a polyacetylene derivative, a polythiophene derivative, a polythienylene vinylene derivative, Polyphenylene derivatives, polyphenylene vinylene derivatives, polypyrrole derivatives, polyaniline derivatives, polyarylamine derivatives, polyquinoline derivatives, perylene derivatives, tetracene derivatives, pentacene derivatives, phthalocyanine derivatives, and the like). In this case, the content of the compound represented by the general formula (1) to the general formula (3) is preferably 20% by mass or more, and more preferably 50% by mass or more.

Furthermore, the organic semiconductor layer may be formed of at least one compound represented by General Formula (1) to General Formula (3) and a polymer compound.
Examples of such polymer compounds 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 derivatives And 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.
In addition, when forming an organic-semiconductor layer using together at least 1 type of compound represented by General formula (1)-General formula (3), and a high molecular compound, General formula (1)-General formula (3) The content of at least one compound represented by) is preferably 5% by mass or more, and more preferably 20% by mass or more with respect to the polymer compound.

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 at least one compound represented by General Formula (1) to General Formula (3) 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 Nitrile solvents such as dinitrile and benzonitrile, organic solvents such as aprotic polar solvents such as dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Can be mentioned. These solvents may be used alone or in combination.
The concentration of at least one compound represented by general formula (1) to general formula (3) in the solvent is not particularly limited, but is generally 0.01 to 20% by mass, more preferably Is preferably adjusted to 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 present invention, after the organic semiconductor layer is formed, a post-treatment may be further performed as desired.
For example, after the organic semiconductor layer is formed, heat treatment may be performed to reduce the distortion of the film thickness generated during the formation or to improve the generated pinholes.
In addition, it may be preferable to perform heat treatment for the purpose of controlling the arrangement and orientation of molecules in the organic semiconductor layer.
Although it does not restrict | limit especially regarding the temperature of heat processing, About room temperature-about 200 degreeC, Preferably, it implements at 40 degreeC-150 degreeC. The heat treatment may be performed in the air or in an inert gas atmosphere such as nitrogen or argon.

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.
Examples of the donor dopant include alkali metals such as Li, Na, K, Rb, and Cs, alkaline earth metals such as Ca, Sr, and Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Rb, Dy, Ho, Er, Yb and other rare earth metals, ammonium ions, R ₄ P ⁺ (R represents an alkyl group), R ₄ As ⁺ (R represents an alkyl group), R ₃ S ⁺ (R represents Represents an alkyl group), and acetylcholine.

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 halogen compounds such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr and IF, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ and SO _3. Lewis acids such as HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H and other organic acids such as acetic acid, formic acid and 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, Ce, Nd, Pr and other lanthanoids and Y ) a transition metal compound, such ^{as, Cl -, Br -, I} -, ClO 4 -, PF 6 -, AsF 5 -, SbF 6 -, BF 4 -, electrolyte anions such as sulfonate anion Etc., and the like.

As a doping method, a method of introducing a dopant after forming an organic semiconductor layer, or a method of introducing a dopant when 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 chloroform solution (concentration: 0.4 mass%) of the compound of Exemplified Compound No. 1-7 was applied thereon, the chloroform was evaporated and the thickness of 80 nm was increased. An organic semiconductor layer made of the compound of Exemplary Compound Nos. 1-7 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.
The threshold voltage of this organic transistor was −12V.
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 13)
In Example 1, when forming the organic semiconductor layer, instead of using the compound of Exemplified Compound No. 1-7, the compound of Exemplified Compound No. 1-10 (Example 2) and the Compound of Exemplified Compound No. 1-17 (Implementation) Example 3), Compound of Example Compound No. 1-23 (Example 4), Compound of Example Compound No. 26 (Example 5), Compound of Example Compound No. 1-29 (Example 6), Example Compound No. 1-33 Compound of Example Compound No. 1-46 (Example 8), compound of Example Compound No. 1-50 (Example 9), compound of Example Compound No. 2-7 (Example 10), Example Compound No. 2-25 (Example 11), Example Compound No. 3-2 (Example 12), Example Compound No. 3-8 (Example 13), Example Compound No. 3-20 (Example 14), Example 1 except that the compound of Example Compound No. 3-23 (Example 15), the compound of Example Compound No. 3-50 (Example 16) and the compound of Example Compound No. 3-57 (Example 17) were used. An organic transistor was produced by the method described in 1.
In addition, the threshold voltage of the organic transistor of Examples 2-13 was the range of -12--16V.
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, in forming the organic semiconductor layer, 2,7-dihexyl [1] benzothieno [3,2-b] [1] benzothiophene was used instead of the compound of Exemplified Compound No. 1-7. Except for the above, an organic transistor was fabricated by the method described in Example 1.
The threshold voltage of the organic transistor was −25V, which was found to be higher than the value of the example.
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 2)
In Example 1, in forming the organic semiconductor layer, 2,7-didodecyl [1] benzothieno [3,2-b] [1] benzothiophene was used instead of using the compound of Exemplified Compound No. 1-7. Except for the above, an organic transistor was fabricated by the method described in Example 1.
In addition, the threshold voltage of this organic transistor was −22V, which was found to be higher than the value of the example.
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 18)
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 Example Compound No. 1-1 is deposited to a thickness of 40 nm at a deposition rate of 0.03 nm / sec to form an organic semiconductor layer. did. Further, a source electrode and a drain electrode were formed thereon by vapor-depositing gold using a mask. The source and drain electrodes had a thickness of 40 nm, a channel width of 5 mm, and a channel length of 30 μm.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 2.5 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 2.1. × 10 ⁸
The threshold voltage of this organic transistor was −13V.

(Example 19)
In Example 18, the organic semiconductor layer was formed by the method described in Example 18 except that the compound of Exemplified Compound No. 1-4 was used instead of the compound of Exemplified Compound No. 1-1. A transistor was manufactured.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 5.8 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 2.7. × 10 ⁸ The threshold voltage of this organic transistor was −12V.

(Example 20)
In Example 18, the organic semiconductor layer was formed by the method described in Example 18 except that the compound of exemplary compound number 2-4 was used instead of the compound of exemplary compound number 1-1. A transistor was manufactured.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 5.3 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 2.4. × 10 ⁸ The threshold voltage of this organic transistor was −16V.

(Example 21)
In Example 18, the organic semiconductor layer was formed by the method described in Example 18 except that the compound of exemplary compound number 3-17 was used instead of the compound of exemplary compound number 1-1. A transistor was manufactured.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 7.7 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 2.8. × 10 ⁷ The threshold voltage of this organic transistor was -11V.

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, an organic transistor of the organic semiconductor layer is made of the general formula (1) to the compound represented by the general formula (3).

Wherein each _{X 1} and _{X 2} independently represents a linear alkyl group having a carbon number of 5-9, a straight chain alkoxy group of 5-9 carbon atoms, an alkoxyalkyl group of linear 5-9 carbon atoms , or represents a linear alkoxyalkoxy group having 5 to 9 carbon atoms]

[Wherein X ₃ and X ₄ simultaneously represent an n-butyl group or a 3-methoxypropyl group ]

[Wherein, X ₅ represents a fluorine atom, and X ₇ represents a 7-ethoxyheptyl group, or X ₅ represents a ₅ -ethoxypentyl group, and X ₇ represents a 5-ethoxypentyl group (provided that X ₆ and X ₈ represents a hydrogen atom, and a represents 0) ]

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