JP2017199828A - Organic transistor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic transistor having high charge mobility, a large current on/off ratio, a low threshold voltage, and excellent storage stability (moist heat resistance).SOLUTION: The organic transistor has an organic semiconductor layer. The organic semiconductor layer contains at least one compound selected from compounds represented by general formula (1) (where Xto Xeach independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group).SELECTED DRAWING: None

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 in that the manufacturing cost increases.
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 drawbacks, for example, an organic transistor using a compound of the formula (A) in an organic semiconductor layer has been proposed (Patent Document 1).

For example, an organic transistor using a compound of the formula (B) in an organic semiconductor layer has been proposed (Patent Document 2).

Further, for example, an organic transistor using a compound of the formula (C) or the formula (D) for an organic semiconductor layer has been proposed (Patent Document 3).

式（Ａ）、式（Ｂ）、式（Ｃ）、式（Ｄ）、式（Ｅ）、および式（Ｆ）の化合物を有機半導体層に用いた有機トランジスタの電荷移動度は高いものの、閾値電圧が高く、さらには保存安定性（耐湿熱性）に難があることが判明した。
現在では、実用化に向け、一層改良された有機トランジスタの開発が求められている。
Further, for example, an organic transistor using a compound of formula (E) or formula (F) in an organic semiconductor layer has been proposed (Patent Document 4).

Although the charge mobility of the organic transistor using the compound of Formula (A), Formula (B), Formula (C), Formula (D), Formula (E), and Formula (F) in the organic semiconductor layer is high, the threshold value It was found that the voltage was high, and further, storage stability (wet heat resistance) was difficult.
At present, development of further improved organic transistors is required for practical use.

JP 2009-54810 A JP 2010-177642 A JP 2015-38044 A JP 2014-139882 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, a low threshold voltage, and excellent storage stability (moisture and heat resistance).

As a result of intensive studies in order to solve the above problems, the inventor of the present invention is an organic transistor comprising at least one compound selected from compounds represented by the general formula (1) in an organic semiconductor layer. The present inventors have found that it has a high degree of current, a large current on / off ratio, a low threshold voltage, and excellent storage stability (moisture and heat resistance), thereby completing the present invention.

（式中、Ｘ_１〜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す）
That is, this invention is an organic transistor which contains at least 1 sort (s) of compound chosen from the compound represented by General formula (1) in this organic-semiconductor layer in the organic transistor which has an organic-semiconductor layer.

(Wherein X _{1 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)

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 (moisture and heat resistance).

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

（式中、Ｘ_１〜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す） Hereinafter, the present invention will be described in detail.
The organic transistor of the present invention comprises an organic semiconductor layer containing at least one compound selected from the compounds represented by the general formula (1).

(Wherein X _{1 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)

X _{1 to} X ₈ in the compound represented by the general formula (1) 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 group, Represents a branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxy group, or a substituted or unsubstituted aryl group;
More preferably, it is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, or a linear 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.

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 addition, in the aryl group, these substituents may be mono-substituted or poly-substituted.

Specific examples of the substituents X _{1 to} X ₈ in the compound represented by 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;

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 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-methoxy-2-propyl group, 3-ethoxypropyl group, 3-ethoxy-2 -Propyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-n-butoxy-2-propyl 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-methoxy Butyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxybutyl 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-methoxy Hexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7- Methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 8-ethoxy group Siooctyl group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxydecyl group, 10-ethoxydecyl group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 11-ethoxyundecyl group, 12 A linear, branched or cyclic alkoxyalkyl group such as methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, 14-methoxytetradecyl group, tetrahydrofurfuryl group;

For example, methoxymethoxy group, ethoxymethoxy 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 2-n-decyloxyethoxy group, 2-n-dodecyloxyethoxy group, 2-n-tetradecyloxyethoxy group, 2-cyclohexyloxyethoxy group, 2-methoxypropoxy group, 3-methoxypropoxy group, 3- Ethoxypropoxy group, 3-ethoxy-2-propoxy group, 3-n-propoxypropoxy group, 3-isopropoxypropoxy group, 3-n-butoxypropoxy group, 3-n-butoxy-2-propoxy group, 3-n -Pentyloxypropoxy group, 3-n-hexyloxypropoxy group, 3- (2'-ethylbutoxy) propoxy group, 3-n-octyloxypropoxy group, 3- (2'-ethylhexyloxy) propoxy group, 3- n-decyloxypropoxy group, 3-n-dodecyloxypropoxy group, 3-n-tetra Siloxypropoxy group, 3-cyclohexyloxypropoxy group, 2-methoxybutoxy group, 3-methoxybutoxy group, 4-methoxybutoxy group, 4-ethoxybutoxy group, 4-n-propoxybutoxy group, 4-isopropoxybutoxy group 4-n-butoxybutoxy group, 4-n-hexyloxybutoxy group, 4-n-octyloxybutoxy group, 4-n-decyloxybutoxy group, 4-n-dodecyloxybutoxy group, 5-methoxypentyloxy Group, 5-ethoxypentyloxy group, 5-n-propoxypentyloxy group, 5-n-pentyloxypentyloxy group, 6-methoxyhexyloxy group, 6-ethoxyhexyloxy group, 6-isopropoxyhexyloxy group, 6-n-butoxyhexyloxy group, 6-n-hexyloxy Sihexyloxy group, 6-n-decyloxyhexyloxy group, 4-methoxycyclohexyloxy group, 7-methoxyheptyloxy group, 7-ethoxyheptyloxy group, 7-isopropoxyheptyloxy group, 8-methoxyoctyloxy group , 8-ethoxyoctyloxy group, 9-methoxynonyloxy group, 9-ethoxynonyloxy group, 10-methoxydecyloxy group, 10-ethoxydecyloxy group, 10-n-butoxydecyloxy group, 11-methoxyundecyl Linear chain such as oxy group, 11-ethoxyundecyloxy group, 12-methoxydodecyloxy group, 12-ethoxydodecyloxy group, 12-isopropoxidedecyloxy group, 14-methoxytetradecyloxy group, tetrahydrofurfuryloxy group Branch or ring Kokishiarukokishi group;

For example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2-n-propylphenyl group, 3-n-propylphenyl group 4-n-propylphenyl group, 4-isopropylphenyl group, 3-n-butylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 2-n-pentyl Phenyl group, 3-n-pentylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 3-n-hexylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 3-n-heptylphenyl group, 4-n-heptylphenyl group, 2-n-octylphenyl group 3-n-octylphenyl group, 4-n-octylphenyl group, 3-n-nonylphenyl group, 4-n-nonylphenyl group, 3-n-decylphenyl group, 4-n-decylphenyl group, 4- n-undecylphenyl group, 3-n-dodecylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,5,6-tetramethyl Phenyl 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, 2-n-butoxy Phenyl group, 3-n-butoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 2-n-hexyloxyphenyl group, 3-n-hexyloxy Phenyl group, 4-n-hexyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 3-n-octyloxyphenyl group, 4-n-octyloxyphenyl group, 4-n- Nonyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-undecyloxyphenyl group, -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, 3-trifluoromethyloxyphenyl group, 4-trifluoromethyloxyphenyl 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-phenyl Phenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) 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, 5 n-butyl-2-furyl group, 5-n-hexyl-2-furyl group, 5-n-octyl-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 Group, 5-phenyl-2-thienyl group, 5- (2′-thienyl) -2-thienyl group, 5- (5′-n-butyl-2′-thienyl) -2-thienyl group, 5- (5 '-N-hexyl-2'-thienyl) -2-thienyl group, 5- (5'-n-decyl-2'-thienyl) -2-thienyl group, 3-thienyl group, 2-pyridyl group, 3- Examples include substituted or unsubstituted aryl groups such as pyridyl group and 4-pyridyl group. Yes.

In the compound represented by the general formula (1), more preferably, X ₁ and X ₂ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a carbon number. 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 carbon Represents a substituted or unsubstituted aryl group of formula 4 to 20, and X _{3 to} X ₈ represent a hydrogen atom,
More preferably, X ₁ and X ₂ 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 2 to 20 carbon atoms. An alkyl group or a substituted or unsubstituted aryl group having 4 to 20 carbon atoms is represented, and X _{3 to} X ₈ represent a hydrogen atom.

  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.

〔式中、Ｘ_１ 〜Ｘ_８は一般式(１)の場合と同じ意味を表し、Ｚ_１ 〜Ｚ_２は脱離基を表す〕 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) can be converted into, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine). Fin) palladium, palladium acetate], or a copper catalyst (eg, copper chloride, copper bromide) can be produced by reacting in the presence of a base, optionally a ligand (eg, a phosphorus compound) [eg, , J. Org. Chem., 72, 5119 (2007), Angew. Chem. Int. Ed., 42, 5400 (2003), Coord. Chem. Rev., 248, 2337 (2004). Can be).

[Wherein, X _{1 to} X ₈ represent the same meaning as in the general formula (1), and Z _{1 to} Z ₂ represent a leaving group]

In addition, the compound represented by the general formula (1) is, for example, a compound represented by the general formula (3), the general formula (4), the general formula (5), or the general formula (6), for example, an acid ( For example, it can be produced by the action of polyphosphoric acid or hydrogen bromide (for example, the method described in Chem. Rev., 87, 1277 (1987) can be referred to).

〔式中、Ｘ_１ 〜Ｘ_８は一般式（１）の場合と同じ意味を表す〕

[Wherein X _{1 to} X ₈ represent the same meaning as in the general formula (1)]

In the general formula (2), Z _{1 to} Z ₂ each represent a leaving group, preferably a halogen atom or —OSO ₂ —R group, and more preferably a halogen atom.
The halogen atom that is a preferred leaving group represented by Z _{1 to} Z ₂ is a fluorine atom, 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 ₂ , 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 ₈ 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 preferable leaving group represented by Z _{1 to} Z ₂ , a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group is more preferable. It is.

  In addition, the compound represented by the general formula (1) according to the present invention may be produced in a mold that forms a solvate with a solvent used (for example, an aromatic hydrocarbon solvent such as toluene). However, in the organic transistor of the present invention, such a solvate as well as a non-solvate of the compound represented by the general formula (1) can be used.

  When the compound represented by the general formula (1) is used in an organic transistor, a purification method such as a recrystallization method, a column chromatography method, a sublimation purification method, or a combination of these methods increases the purity. It is preferred to use

The organic transistor of the present invention is characterized in that the organic semiconductor layer contains at least one compound represented by the general formula (1), which has a high charge mobility, which is unconventional, It is possible to provide an organic transistor having a large on / off ratio, a low threshold voltage, and excellent storage stability.
The compound represented by the general formula (1) in the organic semiconductor layer may be in an amorphous or crystalline form, and more preferably in a crystalline form.
The crystal may be in a single crystal state or a polycrystalline state.

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). It contains at least one compound represented by

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.
Furthermore, the organic transistor of the present invention can take the form of a vertical organic transistor or a stepped organic transistor [for example, described in Applied Physics, Vol. 79, 993 (2010)].

  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, paper, ceramic, plastic substrate, etc. 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, 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, Metals and alloys such as chromium / molybdenum alloy, aluminum / lithium alloy, aluminum / scandium / lithium alloy, sodium / potassium alloy, fluorine doped zinc oxide, silicon single crystal with improved conductivity , Silicon-based materials such as polycrystalline silicon and amorphous silicon, carbon materials such as carbon black, graphite, and glassy carbon, and more preferably, indium tin oxide alloy, gold, silver, platinum, copper, 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. In addition, ink containing conductive polymer and conductive fine particles, conductive paste (silver paste, gold paste, carbon paste, etc.) are patterned by printing methods such as relief printing, intaglio printing, planographic printing, screen printing, gravure printing, and ink jet printing. It is also possible to use a method of

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.

  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, perfluorooctanethiol, for example, 4-fluorothiophenol. 2,4,6-trifluorothiophenol, 2,3,5,6-tetrafluorothiophenol, pentafluorothiophenol, 4-trifluoromethylthiophenol, 3,5-bistrifluoromethylthiophenol, 4-nitrothio It may be modified with an aromatic thiol compound such as phenol.

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.
As the inorganic insulator, 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, poly (perfluoroalkenyl vinyl ether), parylene, 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 comprises at least one compound represented by the general formula (1) in the organic semiconductor layer, and the compound represented by the general formula (1) is singly used alone. You may use, and may use multiple types together.

Furthermore, the organic semiconductor layer includes at least one compound represented by the general formula (1) and another carrier transporting compound (for example, polyacetylene derivative, polythiophene derivative, polythienylene vinylene derivative, polyphenylene derivative, polyphenylene vinylene derivative). , 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) 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 the general formula (1) 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 (vinyl). Cyclohexane) derivative, polystyrene derivative, poly (4-methylstyrene) derivative, poly (α-methylstyrene) derivative, poly (α-vinylnaphthalene) derivative, poly (vinyltoluene) derivative, poly (chlorotrifluoroethylene) derivative, Poly (4-vinylbiphenyl) derivatives, poly (2-methyl-1,3-butadiene) derivatives, poly (styrene / acrylonitrile) copolymers, poly (styrene / butadiene) copolymers, polyvinyl chloride Derivatives, polyethylene terephthalate derivatives, polybutylene terephthalate derivatives, nylon derivatives, polyester derivatives, polyimide derivatives, polyphenol derivatives, cellulose derivatives, vinylon derivatives, and the like.

These polymer compounds may be used alone or in combination.
In addition, when forming an organic-semiconductor layer using together at least 1 type of compound represented by General formula (1), and a high molecular compound, containing at least 1 type of compound represented by General formula (1) The amount is preferably 5% by mass or more, more preferably 20% by mass or more based on 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 And wet processes such as

When the organic semiconductor layer is formed by a wet process, a solution in which at least one compound represented by the general formula (1) is dissolved or dispersed in a solvent is used.

Examples of the solvent include water, methanol, ethanol, isopropyl alcohol, butanol, hexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, 1,2-propanediol, 1,3-propanediol, octafluoropentanol, and pentafluoro. Alcohol solvents such as propanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone, propiophenone, ester solvents such as ethyl acetate, butyl acetate and γ-butyrolactone, diethyl ether, Ether solvents such as dibutyl ether, dioxane, tetrahydrofuran, cyclopentyl methyl ether, anisole, dimethoxybenzene, hexane, heptane, octene Hydrocarbon solvents such as tan, decane, toluene, xylene, ethylbenzene, cumene, mesitylene, 1,2,3,4-tetrahydronaphthalene, indane, phenylcyclohexane, decahydronaphthalene, trimethylcyclohexane, bicyclohexyl, dichloromethane, chloroform, Halogenated hydrocarbon solvents such as dichloroethane, tetrachloroethane, tetrachloroethylene, chlorobenzene, fluorobenzene, dichlorobenzene, and trichlorobenzene, nitrile solvents such as acetonitrile, propionitrile, methoxyacetonitrile, glutarodinitrile, and benzonitrile, dimethyl sulfone Oxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1, - it can be exemplified dimethyl-2-imidazolidinone, an organic solvent such as an aprotic polar solvent such as tetramethylurea. These solvents may be used alone or in combination.
The concentration of the at least one compound represented by the general formula (1) in the solvent is not particularly limited, but is generally 0.01 to 20% by mass, more preferably 0.05 to It is preferable to adjust to about 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,
Rare earth metals such as Eu, Gd, Tb, Dy, Ho, Er, Yb, ammonium ions,
Examples include R ₄ P ⁺ (R represents an alkyl group), R ₄ As ⁺ (R represents an alkyl group), R ₃ S ⁺ (R represents an alkyl group), acetylcholine, and the like.

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 acceptor dopants include Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ ,
Halogen compounds such as IBr and IF, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ ,
Lewis acids such as BBr ₃ and SO ₃ , HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ ,
Protic acids such as FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, organic acids such as acetic acid, formic acid 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,
Lanthanoids such as Ce, Nd, Pr and transition metal compounds such as Y), Cl ⁻ , Br ⁻ ,
Examples thereof include electrolyte anions such as I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₅ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ and sulfonate anions.
As a doping method, a method of introducing a dopant after forming an organic semiconductor layer, or a method of introducing a dopant at the time of forming the organic semiconductor layer can be applied.

In addition, the organic transistor of the present invention can be provided with a gas barrier layer on the whole or a part of the outer peripheral surface of the organic transistor for the purpose of reducing the influence of oxygen, moisture, etc. in the atmosphere. Examples of the material forming the gas barrier layer include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, poly (perfluoroalkenyl vinyl ether), and the like. 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.
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, the compound of Exemplified Compound No. 7 was deposited in a thickness of 30 nm under vacuum (5 × 10 ⁻⁴ Pa) at a deposition rate of 0.03 nm / sec to form an organic semiconductor layer. Further, a source electrode and a drain electrode were formed thereon by vapor-depositing gold using a mask. The source electrode and drain electrode had a thickness of 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.
The threshold voltage of this organic transistor was −14V.
Furthermore, the fabricated device was stored for 24 hours in an atmosphere of 40 ° C. and a relative humidity of 80%, and then the charge mobility and the on / off ratio of the current were measured in the same manner. The measurement results are shown in Table 1.

(Examples 2 to 8)
In Example 1, instead of using the compound of Exemplified Compound No. 7 in forming the organic semiconductor layer, the compound of Exemplified Compound No. 11 (Example 2), the Compound of Exemplified Compound No. 29 (Example 3), and the Exemplified Compound Compound of Example 42 (Example 4), Compound of Example Compound No. 44 (Example 5), Compound of Example Compound No. 45 (Example 6), Compound of Example Compound No. 47 (Example 7), Example Compound No. 51 An organic transistor was produced by the method described in Example 1 except that the compound (Example 8) was used.
The produced organic transistor exhibited characteristics as a p-type transistor element.
Furthermore, the characteristics of the organic transistor were examined by the method described in Example 1 immediately after fabrication and after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity. The results are shown in Table 1.
In addition, the threshold voltage of the organic transistor immediately after manufacture in Examples 2-8 was -13 to -16V.

(Comparative Example 1)
In Example 1, an organic transistor was produced by the method described in Example 1 except that pentacene was used instead of the compound of Exemplified Compound No. 7 in 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. The produced organic transistor exhibited characteristics as a p-type transistor element. In addition, after being stored for 24 hours in an atmosphere of 40 ° C. and a relative humidity of 80%, the characteristics as an organic transistor were not exhibited.

(Comparative Example 2)
In Example 1, an organic transistor was produced by the method described in Example 1 except that α-hexathienylene was used instead of the compound of Exemplified Compound No. 7 in forming the organic semiconductor layer.
The produced organic transistor exhibited characteristics as a p-type transistor element.
Further, by the method described in Example 1, the characteristics of the organic transistor were examined immediately after production and after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity. The results are shown in Table 1.

この有機トランジスタの閾値電圧は−２１Ｖであり、実施例の値と比べ高い電圧であった。さらに、実施例１に記載の方法により、作製直後、および４０℃、相対湿度８０％の雰囲気下で、２４時間保管後の有機トランジスタの特性を調べ、結果を第１表に示した。 (Comparative Example 3)
In Example 1, the formation of the organic semiconductor layer described in Example 1 except that the compound of formula (A) (the compound described in Patent Document 1) was used instead of the compound of Exemplified Compound No. 7. Thus, an organic transistor was produced.
The produced organic transistor exhibited characteristics as a p-type transistor element.

The threshold voltage of this organic transistor was -21 V, which was higher than the value of the example. Further, by the method described in Example 1, the characteristics of the organic transistor were examined immediately after production and after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity. The results are shown in Table 1.

この有機トランジスタの閾値電圧は−２２Ｖであり、実施例の値と比べ高い電圧であった。さらに、実施例１に記載の方法により、作製直後、および４０℃、相対湿度８０％の雰囲気下で、２４時間保管後の有機トランジスタの特性を調べ、結果を第１表に示した。 (Comparative Example 4)
In Example 1, the formation of the organic semiconductor layer described in Example 1 except that the compound of formula (B) (the compound described in Patent Document 2) was used instead of the compound of Exemplified Compound No. 7. Thus, an organic transistor was produced.
The produced organic transistor exhibited characteristics as a p-type transistor element.

The threshold voltage of this organic transistor was −22V, which was higher than the value of the example. Further, by the method described in Example 1, the characteristics of the organic transistor were examined immediately after production and after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity. The results are shown in Table 1.

この有機トランジスタの閾値電圧は、−２３Ｖであり、実施例の値と比べ高い電圧であった。さらに、実施例１に記載の方法により、作製直後、および４０℃、相対湿度８０％の雰囲気下で、２４時間保管後の有機トランジスタの特性を調べ、結果を第１表に示した。 (Comparative Example 5)
In Example 1, in forming the organic semiconductor layer, the compound of formula (C) (the compound described in Patent Document 3) was used instead of the compound of Exemplified Compound No. 7, as described in Example 1. Thus, an organic transistor was produced.
The produced organic transistor exhibited characteristics as a p-type transistor element.

The threshold voltage of this organic transistor was −23 V, which was higher than the value of the example. Further, by the method described in Example 1, the characteristics of the organic transistor were examined immediately after production and after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity. The results are shown in Table 1.

この有機トランジスタの閾値電圧は、−２５Ｖであり、実施例の値と比べ高い電圧であった。さらに、実施例１に記載の方法により、作製直後、および４０℃、相対湿度８０％の雰囲気下で、２４時間保管後の有機トランジスタの特性を調べ、結果を第１表に示した。 (Comparative Example 6)
In Example 1, the organic semiconductor layer was formed as described in Example 1 except that the compound of the formula (E) (the compound described in Patent Document 4) was used instead of the compound of Exemplified Compound No. 7. Thus, an organic transistor was produced.
The produced organic transistor exhibited characteristics as a p-type transistor element.

The threshold voltage of this organic transistor was −25V, which was higher than the value of the example. Further, by the method described in Example 1, the characteristics of the organic transistor were examined immediately after production and after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity. The results are shown in Table 1.

Example 9
A thermal oxide film (SiO ₂ ) having a thickness of 200 nm was formed on a silicon substrate having a resistivity of 0.02 Ω · cm as a gate electrode. Here, the silicon substrate itself becomes the gate electrode, and the SiO ₂ layer formed on the surface of the silicon substrate becomes the gate insulating layer. The silicon substrate is heated to 80 ° C., a chlorobenzene solution (concentration: 0.5 mass%) of the compound of Exemplified Compound No. 15 is applied on the silicon substrate, and the chlorobenzene is evaporated to give an Exemplified Compound No. of 50 nm thickness. An organic semiconductor layer made of 15 compounds 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.
The produced organic transistor exhibited characteristics as a p-type transistor element.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the charge mobility was 4.6 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 4. It was 8 × 10 ⁶ . The threshold voltage of this organic transistor was −15V.
The charge mobility of the organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity is 3.7 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio is 4 0.2 × 10 ⁶ .

(Example 10)
In Example 9, an organic transistor was prepared by the method described in Example 9 except that the compound of Exemplified Compound No. 15 was used instead of the compound of Exemplified Compound No. 15 in forming the organic semiconductor layer. . The produced organic transistor exhibited characteristics as a p-type transistor element.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 5.5 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 5.7 ×. 10 ⁶ . The threshold voltage of this organic transistor was −13V. The charge mobility of the organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity is 4.4 × 10 ^−1.
(cm ² / Vsec), and the on / off ratio of the current was 4.8 × 10 ⁶ .

(Example 11)
In Example 9, when forming the organic semiconductor layer, an organic transistor was produced by the method described in Example 9 except that the compound of Exemplified Compound No. 34 was used instead of the compound of Exemplified Compound No. 15 .
The produced organic transistor exhibited characteristics as a p-type transistor element.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 6.9 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 6.0. × 10 ⁶ The threshold voltage of this organic transistor was −14V. The charge mobility of the organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity is 5.4 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio is 5 It was 3 × 10 ⁶ .

Example 12
In Example 9, an organic transistor was produced by the method described in Example 9 except that the compound of Example Compound No. 15 was used instead of the compound of Example Compound No. 15 in forming the organic semiconductor layer. .
The produced organic transistor exhibited characteristics as a p-type transistor element.
Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 5.2 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 5.7. × 10 ⁶ The threshold voltage of this organic transistor was −13V. The charge mobility of the organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity is 4.2 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio is 4 0.6 × 10 ⁶ .

(Example 13)
In Example 9, an organic transistor was produced by the method described in Example 9 except that the compound of Example Compound No. 15 was used instead of the compound of Example Compound No. 15 in forming the organic semiconductor layer. .
The produced organic transistor exhibited characteristics as a p-type transistor element.
Furthermore, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 6.6 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 6.2. × 10 ⁶ The threshold voltage of this organic transistor was −13V. The charge mobility of the organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity is 5.3 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio is 5 0.0 × 10 ⁶ .

(Example 14)
In Example 9, an organic transistor was produced by the method described in Example 9 except that the compound of exemplary compound number 59 was used instead of the compound of exemplary compound number 15 in forming the organic semiconductor layer. . The produced organic transistor exhibited characteristics as a p-type transistor element. Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 5.6 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 5.3. × 10 ⁶ The threshold voltage of this organic transistor was −15V. The charge mobility of the organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity is 4.5 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio is 4 0.2 × 10 ⁶ .

さらに、実施例１に記載の方法により、有機トランジスタの特性を調べたところ、移動度は、２.３×１０^−１(ｃｍ^２／Ｖｓｅｃ)であり、電流のオン／オフ比は４.５×１０^５であった。この有機トランジスタの閾値電圧は、−２３Ｖであった。尚、４０℃、相対湿度８０％の雰囲気下で、２４時間保管後の有機トランジスタの電荷移動度は１.２×１０^−１(ｃｍ^２／Ｖｓｅｃ）、電流のオン／オフ比は２.６×１０^５であり、保存安定性は不良であることが判明した。 (Comparative Example 7)
In Example 9, in forming the organic semiconductor layer, the compound of formula (D) (the compound described in Patent Document 3) was used instead of the compound of Exemplified Compound No. 15, as described in Example 9. Thus, an organic transistor was produced. The produced organic transistor exhibited characteristics as a p-type transistor element.

Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 2.3 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 4.5. × 10 ⁵ The threshold voltage of this organic transistor was −23V. The organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity has a charge mobility of 1.2 × 10 ⁻¹ (cm ² / Vsec), and a current on / off ratio of 2.6. × a ^105, storage stability is poor has been found.

さらに、実施例１に記載の方法により、有機トランジスタの特性を調べたところ、移動度は、３.３×１０^−１(ｃｍ^２／Ｖｓｅｃ)であり、電流のオン／オフ比は４.５×１０^５であった。この有機トランジスタの閾値電圧は、−２２Ｖであった。尚、４０℃、相対湿度８０％の雰囲気下で、２４時間保管後の有機トランジスタの電荷移動度は１.７×１０^−１（ｃｍ^２／Ｖｓｅｃ）、電流のオン／オフ比は２.４×１０^５であり、保存安定性は不良であることが判明した。 (Comparative Example 8)
In Example 9, the organic semiconductor layer was formed as described in Example 9 except that the compound of the formula (F) (the compound described in Patent Document 4) was used instead of the compound of Exemplified Compound No. 15. Thus, an organic transistor was produced.
The produced organic transistor exhibited characteristics as a p-type transistor element.

Further, when the characteristics of the organic transistor were examined by the method described in Example 1, the mobility was 3.3 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio was 4.5. × 10 ⁵ The threshold voltage of this organic transistor was −22V. In addition, the charge mobility of the organic transistor after storage for 24 hours in an atmosphere of 40 ° C. and 80% relative humidity is 1.7 × 10 ⁻¹ (cm ² / Vsec), and the current on / off ratio is 2.4. × a ^105, storage stability is poor has been found.

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 the threshold voltage is −13 to −16 V as described above. It is clear that the organic transistor has excellent characteristics as an organic transistor, and has excellent storage stability (moisture and heat resistance).

The organic transistor of the present invention has high charge mobility, a large current on / off ratio, a low threshold voltage, and excellent storage stability (moisture and heat resistance). A liquid crystal display element, an organic electroluminescent element, It can be used for 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 the general formula (1).

(Wherein X _{1 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)

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