JP5634751B2 - Organic transistor - Google Patents

Description

The present invention relates to an organic transistor. More specifically, the present invention relates to an organic transistor using a specific organic compound in 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.
Further, it is described that dibenzo [a, j] naphthacene and dibenzo [de, qr] naphthacene are useful for an organic semiconductor layer of an organic transistor (Patent Document 1). However, it has been found that organic transistors using these dibenzonaphthacenes in the organic semiconductor layer have a problem of low charge mobility.
In addition, an organic transistor using 2,8-diphenyl-peri-xanthenoxanthene as an organic semiconductor layer has been proposed (Patent Document 2). However, an organic transistor using a 2,8-diphenyl-peri-xanthenoxanthene compound for the organic semiconductor layer has a drawback of low charge mobility.
At present, development of further improved organic transistors is required for practical use.

JP 2005-519486 A JP 2009-29746 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.

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, and excellent storage stability, and the present invention was completed.
That is, the present invention
An organic transistor having an organic semiconductor layer, wherein the organic semiconductor layer contains at least one compound selected from compounds represented by formulas (1) to (3).

（式中、Ｘ_１〜Ｘ_４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、Ｙ_１およびＹ_２はそれぞれ独立に、酸素原子または硫黄原子を表し、環Ａは置換または未置換のベンゼン環、置換または未置換のチオフェン環、あるいは置換または未置換のベンゾ［ｂ］チオフェン環を表し、環Ｂは置換または未置換のチオフェン環、あるいは置換または未置換のベンゾ［ｂ］チオフェン環を表す）

Wherein X _{1 to} X ₄ 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, Y ₁ and Y ₂ each independently represent an oxygen atom or a sulfur atom, and ring A represents a substituted or unsubstituted benzene A ring, a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted benzo [b] thiophene ring, and ring B represents a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted benzo [b] thiophene ring )

（式中、Ｘ_１１〜Ｘ_２４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、さらに、隣接するＸ_１１〜Ｘ_１８は互いに結合して置換または未置換のベンゼン環を形成していてもよく、Ｙ_１１およびＹ_１２はそれぞれ独立に、酸素原子または硫黄原子を表す）

Wherein X _{11 to} X ₂₄ 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, and adjacent X _{11 to} X ₁₈ may be bonded to each other to form a substituted or unsubstituted benzene ring. Well, Y ₁₁ and Y ₁₂ each independently represent an oxygen atom or a sulfur atom)

（式中、Ｒ_０およびＲ_００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、ＡおよびＢはそれぞれ独立に、置換または未置換のチエノチエニレン基を表し、ａは０または１を表す）

Wherein R ₀ and R ₀₀ 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, A and B each independently represent a substituted or unsubstituted thienothienylene group, and a represents 0 or 1)

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.

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

（式中、Ｘ_１〜Ｘ_４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、Ｙ_１およびＹ_２はそれぞれ独立に、酸素原子または硫黄原子を表し、環Ａは置換または未置換のベンゼン環、置換または未置換のチオフェン環、あるいは置換または未置換のベンゾ［ｂ］チオフェン環を表し、環Ｂは置換または未置換のチオフェン環、あるいは置換または未置換のベンゾ［ｂ］チオフェン環を表す）

Wherein X _{1 to} X ₄ 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, Y ₁ and Y ₂ each independently represent an oxygen atom or a sulfur atom, and ring A represents a substituted or unsubstituted benzene A ring, a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted benzo [b] thiophene ring, and ring B represents a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted benzo [b] thiophene ring )

（式中、Ｘ_１１〜Ｘ_２４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、さらに、隣接するＸ_１１〜Ｘ_１８は互いに結合して置換または未置換のベンゼン環を形成していてもよく、Ｙ_１１およびＹ_１２はそれぞれ独立に、酸素原子または硫黄原子を表す）

Wherein X _{11 to} X ₂₄ 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, and adjacent X _{11 to} X ₁₈ may be bonded to each other to form a substituted or unsubstituted benzene ring. Well, Y ₁₁ and Y ₁₂ each independently represent an oxygen atom or a sulfur atom)

（式中、Ｒ_０およびＲ_００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、ＡおよびＢはそれぞれ独立に、置換または未置換のチエノチエニレン基を表し、ａは０または１を表す）

Wherein R ₀ and R ₀₀ 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, A and B each independently represent a substituted or unsubstituted thienothienylene group, and a represents 0 or 1)

[Compound of general formula (1)]
In the compound represented by the general formula (1), X _{1 to} X ₄ 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.
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 to} X ₄ 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.

Specific examples of X _{1 to} X ₄ in the general formula (1) include, for example, a hydrogen atom; for example, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom;
For example, methyl group, ethyl group, 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-heptyl group, 3 , 5,5-trimethylhexyl group, n-decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group 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, Linear, branched or cyclic alkyl groups such as 4-tert-butylcyclohexyl group, cycloheptyl group, 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, ethoxymethoxy group, 1-methoxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 2-isopropoxyethoxy group, 2-n-butoxyethoxy group, 2-n -Hexyloxyethoxy group, 2-n-octyloxyethoxy group, 2- (2'-ethylhexyloxy) ethoxy group, 2-n-decyloxyethoxy group, 2-methoxypropoxy group, 3-methoxypropoxy group, 3- Ethoxypropoxy group, 3-isopropoxypropoxy group, 3-n-butoxypropoxy group, 3-n-hexyloxypropoxy group, 3-n-octyloxypropoxy group, 2-methoxybutoxy group, 3-methoxybutoxy group, 4 -Methoxybutoxy group, 4-ethoxybutoxy group, 4-isopropoxybutoxy Group, 4-n-butoxybutoxy group, 4-n-hexyloxybutoxy group, 4-n-decyloxybutoxy group, 4-n-dodecyloxybutoxy group, 5-ethoxypentyloxy group, 6-methoxyhexyloxy group 6-ethoxyhexyloxy group, 6-isopropoxyhexyloxy group, 4-methoxycyclohexyloxy group, 7-methoxyheptyloxy group, 8-ethoxyoctyloxy group, 10-methoxydecyloxy group, 12-ethoxydodecyloxy group Linear, branched or cyclic alkoxyalkoxy groups such as

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.
In the general formula (1), X _{1 to} X ₄ are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, and a straight chain having 1 to 16 carbon atoms. Chain, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group having 2 to 16 carbon atoms, linear, branched or cyclic alkoxyalkoxy group having 2 to 16 carbon atoms, or 6 to 20 carbon atoms an aryl group, more preferably, X ₁ to X ₄ is a hydrogen atom.

In the compound represented by the general formula (1), Y ₁ and Y ₂ each independently represent an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
In the compound represented by the general formula (1), ring A represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted benzo [b] thiophene ring,
Preferably, 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 linear, branched or cyclic alkoxyalkoxy group, or a substituent Or a benzene ring optionally substituted with an unsubstituted aryl group,
Halogen atom, linear, branched or cyclic alkyl group, linear, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group, linear, branched or cyclic alkoxyalkoxy group, or substituted or unsubstituted A thiophene ring optionally substituted with an aryl group, 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 linear Represents a benzo [b] thiophene ring which may be substituted with a branched or cyclic alkoxyalkoxy group or a substituted or unsubstituted aryl group.
Ring A is more preferably 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 linear, branched or cyclic alkoxy group. The thiophene ring which may be substituted by the alkoxy group or the substituted or unsubstituted aryl group is represented.

In the compound represented by the general formula (1), ring B represents a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted benzo [b] thiophene ring,
Preferably, 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 linear, branched or cyclic alkoxyalkoxy group, or a substituent Or a thiophene ring optionally substituted with an unsubstituted aryl group, 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 benzo [b] thiophene ring which may be substituted with a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group.
Ring B is more preferably 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 linear, branched or cyclic alkoxy group. The thiophene ring which may be substituted by the alkoxy group or the substituted or unsubstituted aryl group is represented.
Specific examples of the substituent which may be substituted on ring A and ring B are preferably a halogen atom exemplified by X _{1 to} X ₄ , 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, 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 C4-C20 substituted or unsubstituted aryl group can be illustrated.

The thiophene ring represented by ring A and ring B is preferably a thiophene ring condensed at the 2-position and the 3-position, or a thiophene ring condensed at the 3-position and the 4-position, more preferably the 2-position. A thiophene ring condensed at the 3-position.
The benzo [b] thiophene ring represented by ring A and ring B is preferably a benzo [b] thiophene ring condensed at the 2-position and 3-position.

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

[Method for producing compound of general formula (1)]
The compound represented by the general formula (1) according to the present invention can be produced with reference to a method known per se.
That is, the compound represented by the general formula (1) is converted into, for example, a compound represented by the general formula (4) or the general formula (5), for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride. , Tetrakis (triphenylphosphine) palladium, palladium acetate] can be produced in the presence of a base [for example, Chem. Rev. 107, 174 (2007) can be referred to].

〔式中、Ｘ_１〜Ｘ_４、Ｙ_１、Ｙ_２、環Ａおよび環Ｂは一般式（１）の場合と同じ意味を表し、Ｚ_１〜Ｚ_４は脱離基を表す〕

また、一般式（１）で表される化合物は、例えば、一般式（６）で表される化合物に、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〕、あるいは銅触媒（例えば、塩化銅、臭化銅）を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〔例えば、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．，７２、２３４５（１９９９）、Ｃｏｏｒｄ．Ｃｈｅｍ．Ｒｅｖ．，２４８、２３３７（２００４）に記載の方法を参考にすることができる〕。

[Wherein, X _{1 to} X ₄ , Y ₁ , Y ₂ , ring A and ring B represent the same meaning as in general formula (1), and Z _{1 to} Z ₄ represent leaving groups]

In addition, the compound represented by the general formula (1) can be converted into, for example, a compound represented by the general formula (6) by, for example, palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine). Fin) palladium, palladium acetate] or a copper catalyst (eg, copper chloride, copper bromide) in the presence of a base [see, for example, Bull. Chem. Soc. Jpn. 72, 2345 (1999), Coord. Chem. Rev. , 248, 2337 (2004) can be referred to].

〔式中、Ｘ_１〜Ｘ_４、Ｙ_１、Ｙ_２、環Ａおよび環Ｂは一般式（１）の場合と同じ意味を表し、Ｚ_５およびＺ_６は脱離基を表す〕

尚、一般式（４）〜一般式（６）において、Ｚ_１〜Ｚ_６は脱離基を表し、好ましくは、ハロゲン原子または−ＯＳＯ_２−Ｒ基を表す。
Ｚ_１〜Ｚ_６で表される好ましい脱離基であるハロゲン原子としては、塩素原子、臭素原子、またはヨウ素原子である。

Ｚ_１〜Ｚ_６で表される好ましい脱離基である−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、あるいは炭素数１〜１０の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、さらに好ましくは、炭素数１〜８の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す。

[Wherein, X _{1 to} X ₄ , Y ₁ , Y ₂ , ring A and ring B represent the same meaning as in general formula (1), and Z ₅ and Z ₆ represent a leaving group]

In the general formulas (4) to (6), Z _{1 to} Z ₆ each represent a leaving group, preferably a halogen atom or an —OSO ₂ —R group.
The halogen atom that is a preferred leaving group represented by Z _{1 to} Z ₆ is a chlorine atom, a bromine atom, or an iodine atom.

In the —OSO ₂ —R group which is a preferred leaving group represented by Z _{1 to} Z ₆ , R is a substituted or unsubstituted aryl group, or a linear, branched or cyclic group which may be substituted with a halogen atom Represents an alkyl group, and more preferably represents a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a linear, branched or cyclic alkyl group which may be substituted with a halogen atom having 1 to 10 carbon atoms. More preferably, it represents a linear, branched or cyclic alkyl group which may be substituted with a halogen atom having 1 to 8 carbon atoms.

In the —OSO ₂ —R group, specific examples of the substituted or unsubstituted aryl group represented by R include, for example, the substituted or unsubstituted aryl groups exemplified as X _{1 to} X ₄ in the general formula (1). Can be mentioned.
In -OSO 2 _-R group, straight optionally substituted by halogen atom represented by R, specific examples of the alkyl group branched or cyclic, for example, a methyl group, an ethyl group, 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 group And an alkyl group substituted with a halogen atom such as a dichlorofluoromethyl group, a pentafluoroethyl group, and an n-nonafluorobutyl group.
As the —OSO ₂ —R group, which is a preferred leaving group represented by Z _{1 to} Z ₆ , more preferably, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group. It is.

[Compound of general formula (2)]
In the compound represented by the general formula (2), X _{11 to} X ₂₄ 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.

In the compound represented by the general formula (2), more preferably, X _{11 to} X ₂₄ 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.

Halogen atom of X _{11 to} X ₂₄ in formula (2), linear, branched or cyclic alkyl group, linear, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group, linear, branched Specific examples of the cyclic alkoxyalkoxy group or the substituted or unsubstituted aryl group include, for example, the halogen atom, linear, branched, or exemplified in X _{1 to} X ₄ in the compound represented by the general formula (1). Examples include cyclic alkyl groups, linear, branched or cyclic alkoxy groups, linear, branched or cyclic alkoxyalkyl groups, linear, branched or cyclic alkoxyalkoxy groups, or substituted or unsubstituted aryl groups. it can.

In the general formula (2), X _{11 to} X ₂₄ are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, and a straight chain having 1 to 16 carbon atoms. It is a chain, branched or cyclic alkoxy group, or an aryl group having 6 to 20 carbon atoms.

In the compound represented by the general formula (2), adjacent X _{11 to} X ₁₈ may be bonded to each other to form a substituted or unsubstituted benzene ring.
The formed benzene ring 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. An alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group,
Preferably, 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, a linear, branched or cyclic group having 2 to 20 carbon atoms An alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 4 to 20 carbon atoms.
Specific examples of the substituent that may be substituted on the formed benzene ring include, for example, the halogen atom, linear, branched, or cyclic exemplified in X _{1 to} X ₄ in the compound represented by the general formula (1). And an alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group. .

In the compound represented by the general formula (2), Y ₁₁ and Y ₁₂ each independently represent an oxygen atom or a sulfur atom, and more preferably Y ₁₁ and Y ₁₂ simultaneously represent an oxygen atom or a sulfur atom.

Specific examples of the compound represented by the general formula (2) according to the present invention include the following compounds, but the present invention is not limited thereto.

[Method for producing compound of general formula (2)]
The compound represented by the general formula (2) according to the present invention can be produced with reference to a method known per se.
That is, the compound represented by the general formula (2) can be obtained by, for example, converting a compound represented by the general formula (7) into a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine). Palladium, palladium acetate] can be produced by reacting in the presence of a base [see, for example, Chem. Rev. 107, 174 (2007) can be referred to].

〔式中、Ｘ_１１〜Ｘ_２４、Ｙ_１１およびＹ_１２は一般式(２)の場合と同じ意味を表し、Ｚ_１およびＺ_２はハロゲン原子あるいはトリフルオロメチルスルフォニル基を表す〕

一般式（７）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(２)において、Ｙ_１１およびＹ_１２が酸素原子で表される化合物は、例えば、一般式（８）で表される化合物に、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〕を塩基の存在下、一般式(９)および一般式(１０)で表される化合物を作用させることにより製造することができる〔例えば、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．，７２、２３４５(１９９９)に記載の方法を参考にすることができる〕。

[Wherein, X _{11 to} X ₂₄ , Y ₁₁ and Y ₁₂ represent the same meaning as in the general formula (2), and Z ₁ and Z ₂ represent a halogen atom or a trifluoromethylsulfonyl group]

In the general formula (7), the halogen atom represented by Z ₁ and Z ₂ is preferably a chlorine atom, a bromine atom, or an iodine atom.

In the general formula (2), the compound in which Y ₁₁ and Y ₁₂ are represented by an oxygen atom is, for example, a compound represented by the general formula (8), a palladium catalyst [for example, bis (triphenylphosphine) Palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate] can be produced by reacting the compounds represented by general formula (9) and general formula (10) in the presence of a base [for example, Bull. Chem. Soc. Jpn. 72, 2345 (1999) can be referred to].

〔式中、Ｘ_１１〜Ｘ_２４は一般式（２）の場合と同じ意味を表し、Ｙ_１１およびＹ_１２は酸素原子を表す〕

[Wherein, X _{11 to} X ₂₄ represent the same meaning as in the general formula (2), and Y ₁₁ and Y ₁₂ represent an oxygen atom]

[Compound of general formula (3)]
In the compound represented by the general formula (3), R ₀ and R ₀₀ each independently represents 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.

In the compound represented by the general formula (3), more preferably, R ₀ and R ₀₀ are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. 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 of
More preferably, a hydrogen atom, a halogen atom, a straight chain, branched or cyclic alkyl group having 1 to 16 carbon atoms, a straight chain, branched or cyclic alkoxy group having 1 to 16 carbon atoms, or a straight chain having 2 to 16 carbon atoms. Represents a branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 16 carbon atoms, or a substituted or unsubstituted aryl group having 4 to 16 carbon atoms,
More preferably, it is a hydrogen atom, a halogen atom, a straight chain, branched or cyclic alkyl group having 1 to 16 carbon atoms, a straight chain, branched or cyclic alkoxy group having 1 to 16 carbon atoms, or a straight chain having 2 to 16 carbon atoms. A branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 16 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 16 carbon atoms, a substituted or unsubstituted group having 10 to 16 carbon atoms Or a substituted or unsubstituted thienyl group having 4 to 16 carbon atoms.

R ₀ and R ₀₀ halogen atom in general formula (3), linear, branched or cyclic alkyl group, linear, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group, linear, branched Specific examples of the cyclic alkoxyalkoxy group or the substituted or unsubstituted aryl group include, for example, the halogen atom, linear, branched, or exemplified in X _{1 to} X ₄ in the compound represented by the general formula (1). Examples include cyclic alkyl groups, linear, branched or cyclic alkoxy groups, linear, branched or cyclic alkoxyalkyl groups, linear, branched or cyclic alkoxyalkoxy groups, or substituted or unsubstituted aryl groups. it can.

In the compound represented by the general formula (3), A and B each independently represent a substituted or unsubstituted thienotienylene group,
Preferably, thieno [3,2-b] thiophene-2,5-diyl group represented by formula (A-1) or thieno [2,3-b] thiophene represented by formula (A-2) Represents a -2,5-diyl group.

（式中、Ｒ_１〜Ｒ_４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）

式（Ａ−１）〜式（Ａ−２）において、Ｒ_１〜Ｒ_４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、
好ましくは、水素原子、ハロゲン原子、炭素数１〜２０の直鎖、分岐または環状のアルキル基、炭素数１〜２０の直鎖、分岐または環状のアルコキシ基、炭素数２〜２０の直鎖、分岐または環状のアルコキシアルキル基、炭素数２〜２０の直鎖、分岐または環状のアルコキシアルコキシ基、あるいは炭素数４〜２０の置換または未置換のアリール基を表し、より好ましくは、水素原子、ハロゲン原子、炭素数１〜１０の直鎖、分岐または環状のアルキル基、あるいは炭素数６〜１０の置換または未置換のアリール基を表し、さらに好ましくは、水素原子を表す。

式（Ａ−１）〜式（Ａ−２）におけるＲ_１〜Ｒ_４のハロゲン原子、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の具体例としては、例えば、一般式（１）で表される化合物におけるＸ₁ 〜Ｘ_４で例示したハロゲン原子、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例示することができる。

Wherein R _{1 to} R ₄ 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)

In formula (A-1) to formula (A-2), R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. Represents a linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group,
Preferably, a hydrogen atom, a halogen atom, a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, a straight chain having 1 to 20 carbon atoms, a branched or cyclic alkoxy group, a straight chain having 2 to 20 carbon atoms, Represents a branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 4 to 20 carbon atoms, more preferably a hydrogen atom, halogen An atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and more preferably a hydrogen atom.

R _{1 to} R ₄ in formula (A-1) to formula (A-2), a halogen atom, 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 are exemplified by X _{1 to} X ₄ in the compound represented by the general formula (1). Halogen atom, linear, branched or cyclic alkyl group, linear, branched or cyclic alkoxy group, linear, branched or cyclic alkoxyalkyl group, linear, branched or cyclic alkoxyalkoxy group, or substituted or unsubstituted The aryl group of can be illustrated.

In the compound represented by the general formula (3), a represents 0 or 1, more preferably 1.
Specific examples of the compound represented by the general formula (3) according to the present invention include the following compounds, but the present invention is not limited thereto.

[Method for producing compound of general formula (3)]
The compound represented by the general formula (3) according to the present invention can be produced with reference to a method known per se.
That is, the compound represented by the general formula (3) includes, for example, a compound represented by the general formula (11) and a compound represented by the general formula (12) and the general formula (13) by a palladium catalyst [for example , Bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium] and a base.
In addition, the compound represented by the general formula (3) includes, for example, a compound represented by the general formula (14) and a compound represented by the general formula (15) and the general formula (16) by using a palladium catalyst [for example, , Bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium] and a base (see, for example, Chem. Rev. 95, 2457 (1995), Chem. Rev. , 102, 1359 (2002), Chem. Rev. 107, 174 (2007); Amer. Chem. Soc. 101, 4992 (1979); Amer. Chem. Soc. , 124, 6343 (2002) can be referred to].

〔式中、Ｒ_０、Ｒ_００、Ａ、Ｂおよびａは一般式（３）の場合と同じ意味を表し、Ｚ_１〜Ｚ_４はハロゲン原子を表し、Ｍ_１〜Ｍ_４は−Ｂ（ＯＲ_１１）（ＯＲ_１２）（式中、Ｒ_１１およびＲ_１２は水素原子またはアルキル基を表し、さらにＲ_１１とＲ_１２が互いに結合して環状のアルキレン基、あるいはアリーレン基を形成していてもよい）、または−Ｓｎ（Ｒ_１３）_３（式中、Ｒ_１３はアルキル基を表す）を表す〕

一般式（１２）、一般式（１３）および一般式（１４）において、Ｍ_１〜Ｍ_４で表される−Ｂ（ＯＲ_１１）（ＯＲ_１２）のＲ_１１およびＲ_１２で表されるアルキル基は、好ましくは、炭素数１〜８のアルキル基を表す。
また、Ｒ_１１およびＲ_１２が互いに結合して環状のアルキレン基を表す場合、好ましくは、炭素数２〜１０の環状のアルキレン基を表す。
また、Ｒ_１１およびＲ_１２が互いに結合してアリーレン基を表す場合、好ましくは、アルキル基で置換されていてもよい炭素数６〜１０の１，２−フェニレン基を表す。
一般式（１２）、一般式（１３）および一般式（１４）において、Ｍ_１〜Ｍ_４で表される−Ｓｎ（Ｒ_１３）_３のＲ_１３で表されるアルキル基は、好ましくは、炭素数１〜６のアルキル基を表す。
一般式（１１）、一般式（１５）および一般式（１６）において、Ｚ_１〜Ｚ_４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、ヨウ素原子を表す。

[Wherein R ₀ , R ₀₀ , A, B and a represent the same meaning as in the general formula (3), Z _{1 to} Z ₄ represent a halogen atom, and M _{1 to} M ₄ represent —B (OR ₁₁ ) (OR ₁₂ ) (wherein R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group, and R ₁₁ and R ₁₂ may be bonded to each other to form a cyclic alkylene group or an arylene group). ), Or -Sn (R ₁₃ ) ₃ (wherein R ₁₃ represents an alkyl group)

Formula (12), in the general formula (13) and the general formula _(14), the alkyl group represented by _{R 11} and _{R 12} of _-B represented by _{M 1 ~M 4 (OR 11)} (OR 12) Preferably represents an alkyl group having 1 to 8 carbon atoms.
In addition, when attached R ₁₁ and R ₁₂ together represents a cyclic alkylene group, preferably represents a cyclic alkylene group having 2 to 10 carbon atoms.
When R ₁₁ and R ₁₂ 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.
Formula (12), in the general formula (13) and the general formula _(14), the alkyl group represented by _{R 13} in -Sn _{(R 13) 3} represented by M 1 ~M ₄ is preferably carbon The alkyl group of number 1-6 is represented.
In the general formula (11), the general formula (15), and the general formula (16), the halogen atom represented by Z _{1 to} Z ₄ preferably represents a chlorine atom, a bromine atom, or an iodine atom.

The compound represented by the general formula (3) is, for example, a compound represented by the general formula (17) and an oxidizing agent (for example, cupric acetate) in the presence of a base (for example, sodium hydroxide). [For example, Bull. Chem. Soc. , 74, 53 (2001) can be referred to].

〔式中、Ｒ_０、Ｒ_００、Ａ、Ｂおよびａは一般式（３）の場合と同じ意味を表す〕

[Wherein R ₀ , R ₀₀ , A, B and a represent the same meaning as in the general formula (3)]

  In addition, the compound represented by the general formula (1) to the general formula (3) according to the present invention is a type in which a solvation with a solvent used in some cases (for example, an aromatic hydrocarbon solvent such as toluene) 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) are used. can do.

[Manufacture of organic transistors]
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.
In the organic transistor of the present invention, the organic semiconductor layer is characterized by containing at least one compound represented by the general formula (1) to the general formula (3). It is possible to provide an organic transistor having high mobility, a large current on / off ratio, and excellent storage stability.
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.

Examples of the electrode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide (IZO), molybdenum oxide, gold, silver, platinum, copper, indium, aluminum, magnesium, nickel, chromium, and 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, as well as fluorine-doped zinc oxide and silicon Examples thereof include silicon-based materials such as crystal, polycrystalline silicon, and amorphous silicon, and carbon materials such as carbon black, graphite, and glassy carbon, and more preferably indium tin oxide alloy, gold, silver, platinum, copper, and indium. Aluminum, silicon material with improved conductivity, and carbon material. 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, 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 the solvent 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, diethyl Ether solvents such as ether, dioxane, tetrahydrofuran and anisole, hydrocarbon solvents such as hexane, octane, toluene, xylene, ethylbenzene, cumene, 1,2,3,4-tetrahydronaphthalene, dichloromethane, chloroform, dichloroethane, tetrachloroethane , Halogenated hydrocarbon solvents such as tetrachloroethylene, chlorobenzene, fluorobenzene, dichlorobenzene, trichlorobenzene, acetonitrile, propio Nitrile solvents such as tolyl, methoxyacetonitrile, glutarodinitrile, benzonitrile, dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other non-protons And organic solvents such as a polar solvent. 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 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.

In addition, the organic transistor of this invention can be used for a liquid crystal display element, an organic electroluminescent element, electronic paper, various sensors, RFID (radio frequency identification cards) etc., for example.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
Examples relating to organic transistors using the compound represented by the general formula (1) in the organic semiconductor layer are shown below.

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. On top of this, under vacuum (5 × 10 ⁻⁴ Pa), the compound of Exemplary Compound No. 1-4 is deposited to a thickness of 30 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 electrode and drain electrode had a thickness of 40 nm, a channel width of 5 mm, and a channel length of 20 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 12)
In Example 1, in forming the organic semiconductor layer, instead of using the compound of Exemplified Compound No. 1-4, the compound of Exemplified Compound No. 1-19 (Example 2), the compound of Exemplified Compound No. 1-22 (Implementation) Example 3), Compound of Example Compound No. 1-37 (Example 4), Compound of Example Compound No. 1-41 (Example 5), Compound of Example Compound No. 1-47 (Example 6), Example Compound No. 1 -55 (Example 7), Example Compound No. 1-74 (Example 8), Example Compound No. 1-98 (Example 9), Example Compound No. 1-103 (Example 10) ), An organic transistor was prepared by the method described in Example 1 except that the compound of Example Compound No. 1-109 (Example 11) and the compound of Example Compound No. 1-117 (Example 12) were used.
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, an organic transistor was fabricated by the method described in Example 1 except that pentacene was used instead of the compound of Exemplary Compound Nos. 1-4 when forming the organic semiconductor layer.
Further, the characteristics of the organic transistor were examined by the method described in Example 1, and the results are shown in Table 1.
In addition, the characteristic as an organic transistor was not shown after leaving for one month.

(Comparative Example 2)
In Example 1, an organic transistor was produced by the method described in Example 1 except that α-hexathienylene was used in place of the compound of Exemplified Compound No. 1-4 when forming the organic semiconductor layer.
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 3)
In Example 1, an organic transistor was formed by the method described in Example 1 except that dibenzo [a, j] naphthacene was used instead of the compound of Exemplified Compound No. 1-4 when forming the organic semiconductor layer. Was made.
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 4)
In Example 1, an organic transistor was formed by the method described in Example 1 except that dibenzo [de, qr] naphthacene was used instead of the compound of Exemplary Compound Nos. 1-4 when forming the organic semiconductor layer. Was made.
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 13)
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: 0.5% by mass) of the compound of Exemplified Compound No. 1-39 was applied on the silicon substrate, the chlorobenzene was evaporated and the thickness of 50 nm was obtained. An organic semiconductor layer made of the compound of Exemplary Compound No. 1-39 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 40 nm, a channel width of 5 mm, and a channel length of 20 μm.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 4.7 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 3.6. × 10 ⁵

(Example 14)
In Example 13, the organic semiconductor layer was formed by the method described in Example 13 except that the compound of Exemplified Compound No. 1-39 was used instead of the compound of Exemplified Compound No. 1-39. A transistor was manufactured.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 3.8 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 3.4. × 10 ⁵

第１表
第１表より、一般式（１）で表される化合物を用いてなる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。

Table 1 From Table 1, the organic transistor using the compound represented by the general formula (1) has high charge mobility, a large current on / off ratio, and has excellent characteristics as an organic transistor. Further, it is clear that the organic transistor is excellent in stability, in which a change with time is suppressed.

Examples relating to organic transistors using the compound represented by the general formula (2) in the organic semiconductor layer are shown below.
(Example 15)
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 Exemplified Compound No. 2-1 is deposited to a thickness of 30 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 electrode and drain electrode had a thickness of 40 nm, a channel width of 5 mm, and a channel length of 20 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 2.

(Examples 16 to 24)
In Example 15, instead of using the compound of Exemplified Compound No. 2-1, in the formation of the organic semiconductor layer, the compound of Exemplified Compound No. 2-5 (Example 16) and the Compound of Exemplified Compound No. 2-17 (Implementation) Example 17), Compound of Example Compound No. 2-26 (Example 18), Compound of Example Compound No. 2-42 (Example 19), Compound of Example Compound No. 2-53 (Example 20), Example Compound No. 2 -59 compound (Example 21), Example compound number 2-77 (Example 22), Example compound number 2-88 (Example 23), Example compound number 2-95 (Example 24) ) Was used to produce an organic transistor by the method described in Example 1.
Further, the characteristics of the organic transistor were examined by the method described in Example 1, and the results are shown in Table 2.

(Example 25)
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: 0.3% by mass) of the compound of Exemplified Compound No. 2-7 was applied thereon, the chlorobenzene evaporated to a thickness of 50 nm. An organic semiconductor layer made of the compound of Exemplary Compound No. 2-7 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 40 nm, a channel width of 5 mm, and a channel length of 20 μm.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 15, the mobility was 8.8 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 3.5. × 10 ⁶

(Example 26)
In Example 25, the organic semiconductor layer was formed by the method described in Example 25 except that the compound of exemplary compound number 2-39 was used instead of the compound of exemplary compound number 2-7. A transistor was manufactured.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 15, the mobility was 6.4 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 4.2. × 10 ⁶

(Example 27)
In Example 25, the organic semiconductor layer was formed by the method described in Example 25 except that the compound of Exemplified Compound No. 2-86 was used instead of the compound of Exemplified Compound No. 2-7. A transistor was manufactured.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 15, the mobility was 1.5 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 2.3. × 10 ⁶

第２表より、一般式（２）で表される化合物を用いてなる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 2, the organic transistor using the compound represented by the general formula (2) has high charge mobility, a large current on / off ratio, and has excellent characteristics as an organic transistor. Further, it is clear that the organic transistor is excellent in stability in which change with time is suppressed.

Examples relating to organic transistors using the compound represented by the general formula (3) in the organic semiconductor layer will be described below.

(Example 28)
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 Exemplified Compound No. 3-9 is deposited at a deposition rate of 0.03 nm / sec to a thickness of 30 nm 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 electrode and drain electrode had a thickness of 40 nm, a channel width of 5 mm, and a channel length of 20 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 3.

(Examples 29 to 33)
In Example 28, instead of using the compound of Exemplified Compound No. 3-9 in the formation of the organic semiconductor layer, the compound of Exemplified Compound No. 3-17 (Example 29) and the Compound of Exemplified Compound No. 3-24 (Implementation) Example 30), the compound of Exemplified Compound No. 3-30 (Example 31), the compound of Exemplified Compound No. 3-53 (Example 32), and the compound of Exemplified Compound No. 3-62 (Example 33) were used. An organic transistor was prepared by the method described in Example 28.
Further, the characteristics of the organic transistor were examined by the method described in Example 28, and the results are shown in Table 3.

(Comparative Example 5)
In Example 28, in forming the organic semiconductor layer, Example 28 was used except that instead of the compound of Exemplified Compound No. 3-9, the compound of the formula (B) (the compound described in Patent Document 2) was used. 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 28, and the results are shown in Table 3.

(Example 34)
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: 0.5 mass%) of the compound of Exemplified Compound No. 3-4 was applied thereon, the chloroform was evaporated and the thickness of 50 nm An organic semiconductor layer made of the compound of Exemplary Compound No. 3-4 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 40 nm, a channel width of 5 mm, and a channel length of 20 μm.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 28, the mobility was 2.2 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 3.4. × 10 ⁵

(Example 35)
In Example 34, the organic semiconductor layer was formed by the method described in Example 34 except that the compound of exemplary compound number 3-11 was used instead of the compound of exemplary compound number 3-4. A transistor was manufactured.
Further, the characteristics of the organic transistor were examined by the method described in Example 28. As a result, the mobility was 6.2 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 4.8. × 10 ⁵

(Example 36)
In Example 34, the organic semiconductor layer was formed by the method described in Example 34 except that the compound of Exemplified Compound No. 3-14 was used instead of the compound of Exemplified Compound No. 3-4. A transistor was manufactured.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 28, the mobility was 5.7 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 4.2. × 10 ⁵

(Example 37)
In Example 34, the organic semiconductor layer was formed by the method described in Example 34 except that the compound of exemplary compound number 3-23 was used instead of the compound of exemplary compound number 3-4. A transistor was manufactured.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 28, the mobility was 7.6 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 3.7. × 10 ⁵

(Example 38)
In Example 34, the organic semiconductor layer was formed by the method described in Example 34, except that the compound of exemplary compound number 3-26 was used instead of the compound of exemplary compound number 3-4. A transistor was manufactured.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 28, the mobility was 3.6 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 3.3. × 10 ⁵

(Example 39)
In Example 34, the organic semiconductor layer was formed by the method described in Example 34, except that the compound of exemplary compound number 3-54 was used instead of the compound of exemplary compound number 3-4. A transistor was manufactured.
Further, when the characteristics of the organic transistor were examined by the method described in Example 28, the mobility was 4.4 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 3.9. × 10 ⁵

(Example 40)
In Example 34, the organic semiconductor layer was formed by the method described in Example 34, except that the compound of exemplary compound number 3-67 was used instead of the compound of exemplary compound number 3-4. A transistor was manufactured.
Further, when the characteristics of the organic transistor were examined by the method described in Example 28, the mobility was 5.6 × 10 ⁻² (cm ² / Vsec), and the current on / off ratio was 4.3. × 10 ⁵

第３表より、一般式（３）で表される化合物を用いてなる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 3, the organic transistor using the compound represented by the general formula (3) has high charge mobility, a large current on / off ratio, and has excellent characteristics as an organic transistor. Further, it is clear that the organic transistor is excellent in stability in which change with time is suppressed.

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) and the like.

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)

An organic transistor having an organic semiconductor layer, wherein the organic semiconductor layer contains at least one compound selected from compounds represented by general formulas (1) to (3).

[Wherein, X _{1 to} X ₄ each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or 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, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms , or an aryl group having 4 to 20 carbon atoms (the halogen atom, It may have a substituent selected from the alkyl group, the alkoxy group, or an aryl group that may be substituted with the halogen atom having 4 to 20 carbon atoms, an alkyl group, or an alkoxy group) ,
Y ₁ and Y ₂ each independently represent an oxygen atom or a sulfur atom,

Ring A is 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, a linear, branched or cyclic group having 2 to 20 carbon atoms. An alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or an aryl group having 4 to 20 carbon atoms (the halogen atom, the alkyl group, the alkoxy group, or the carbon number 4-20). A benzene ring that may be substituted with a halogen atom, an alkyl group, or an aryl group that may be substituted with an alkoxy group .

Halogen atom, straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, straight chain, branched or cyclic alkoxy group having 1 to 20 carbon atoms, straight chain, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms Group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or an aryl group having 4 to 20 carbon atoms (the halogen atom, the alkyl group, the alkoxy group, or the halogen having 4 to 20 carbon atoms). A thiophene ring optionally substituted with an atom, an alkyl group, or a substituent selected from an aryl group optionally substituted with an alkoxy group) ,
Alternatively, 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, a linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms An alkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or an aryl group having 4 to 20 carbon atoms (the halogen atom, the alkyl group, the alkoxy group, or the carbon group having 4 to 20 carbon atoms). A benzo [b] thiophene ring optionally substituted with a halogen atom, an alkyl group, or an aryl group optionally substituted with an alkoxy group (which may have a substituent) .

Ring B is 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, a linear, branched or cyclic group having 2 to 20 carbon atoms. An alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or an aryl group having 4 to 20 carbon atoms (the halogen atom, the alkyl group, the alkoxy group, or the carbon number 4-20). A thiophene ring optionally substituted with a halogen atom, an alkyl group, or an aryl group optionally substituted with an alkoxy group .
Alternatively, 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, a linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms An alkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or an aryl group having 4 to 20 carbon atoms (the halogen atom, the alkyl group, the alkoxy group, or the carbon group having 4 to 20 carbon atoms). A benzo [b] thiophene ring optionally substituted with a substituent selected from a halogen atom, an alkyl group, and an aryl group optionally substituted with an alkoxy group) ]

[Wherein, X _{11 to} X ₂₄ are each independently a hydrogen atom, 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. 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 an aryl group having 4 to 20 carbon atoms (the halogen atom, It may have a substituent selected from the alkyl group, the alkoxy group, or an aryl group that may be substituted with the halogen atom having 4 to 20 carbon atoms, an alkyl group, or an alkoxy group) ,

Further, adjacent X ₁₂ and X ₁₃ , X ₁₃ and X ₁₄ , X ₁₆ and X ₁₇ , and X ₁₇ and X ₁₈ are bonded to each other to form a halogen atom, a linear, branched or cyclic alkyl having 1 to 20 carbon atoms. 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, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms Group or an aryl group having 4 to 20 carbon atoms (from the halogen atom, the alkyl group, the alkoxy group, or an aryl group optionally substituted with the halogen atom, alkyl group, or alkoxy group having 4 to 20 carbon atoms). A benzene ring which may be substituted with (which may have a substituent selected) ,
Y ₁₁ and Y ₁₂ each independently represents an oxygen atom or a sulfur atom.

[Wherein, R ₀ and R ₀₀ are each independently a hydrogen atom, 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. 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 an aryl group having 4 to 20 carbon atoms (the halogen atom, It may have a substituent selected from the alkyl group, the alkoxy group, or an aryl group that may be substituted with the halogen atom having 4 to 20 carbon atoms, an alkyl group, or an alkoxy group) ,
A and B are each independently 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, and a straight chain having 2 to 20 carbon atoms. A chain, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group having 2 to 20 carbon atoms, or an aryl group having 4 to 20 carbon atoms (the halogen atom, the alkyl group, the alkoxy group, or Represents a thienothienylene group optionally substituted with a halogen atom, an alkyl group, or an aryl group optionally substituted with an alkoxy group having 4 to 20 carbon atoms .
a represents 0 or 1]

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