JP2007165484A - Organic semiconductor transistor element, manufacturing method therefor, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic semiconductor transistor element which shows superior solubility and compatibility in a solvent and a resin, is made of a charge transporting material having high carrier mobility, has a high operation speed, and is manufactured easily. <P>SOLUTION: The organic semiconductor transistor element includes source and drain electrodes, an organic semiconductor arranged to be electrically conductive to the source and drain electrodes, and a gate electrode. The organic semiconductor contains one or more kinds of charge transporting polyethers made of a repetition unit containing at least one structure as a partial structure that is selected out of structures represented by at least one or more kinds of the formulas: (AI-1) and (AI-2). In the formulas, the symbol Ar denotes a replaced or nonreplaced single valent benzene ring, a replaced or nonreplaced single valent polynuclear aromatic group hydrocarbon having 2 to 10 aromatic rings, a replaced or nonreplaced single valent condensed aromatic group hydrocarbon having 2 to 10 aromatic rings, or a replaced or nonreplaced single heterocyclic ring; T denotes a two-valent linear hydrocarbon group having 1 to 6 carbon atoms, or a two-valent branch hydrocarbon group having 2 to 10 carbon atoms; m denotes an integer of 0 to 3; and X denotes a substituent represented by the formula (AII). In the formula AII, R<SB>1</SB>to R<SB>6</SB>denotes a replaced or nonreplaced single valent benzene ring, a replaced or nonreplaced single valent polynuclear aromatic group hydrocarbon having 2 to 10 aromatic rings, or a single valent branch hydrocarbon group having 3 to 10 carbon atoms, and n denotes an integer of 1 to 10. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic semiconductor transistor element using an organic semiconductor, a semiconductor device using the organic semiconductor transistor element, and a method for manufacturing the organic semiconductor transistor element. More specifically, the present invention relates to electronic paper or digital paper, an organic EL element, Organic semiconductor transistor element suitable for use in fields such as electrophoretic display elements, drive circuits for display elements such as liquid crystal elements, electronic tags, smart cards, memory elements, gas sensors, and semiconductor devices using the same And a method of manufacturing the organic semiconductor transistor element.

Thin film transistors are widely used as display switching elements such as liquid crystal display elements. Conventionally, a thin film transistor is manufactured using amorphous or polycrystalline silicon. However, manufacturing of a thin film transistor using such silicon uses sputtering, a CVD apparatus, and other manufacturing processes using a vacuum system, which are very expensive. In addition, the manufacturing process of a vacuum system is repeatedly performed to form a thin film transistor, and each layer such as a semiconductor layer is formed. Therefore, an increase in the size of a display device using a thin film transistor has a problem with a significant increase in manufacturing cost. It was.
In addition, the process for forming amorphous or polycrystalline silicon is performed at a very high temperature, and the materials used as the base material are limited. Therefore, there is a problem that a resin substrate having a light weight and flexibility cannot be used.

On the other hand, research on organic semiconductors typified by organic EL elements has been actively conducted in recent years. At the same time, studies have been reported to incorporate organic materials into circuits that have characteristics of lightness and flexibility that are not found in silicon materials.
As an organic substance used for such a thin film transistor, a low molecular compound and a high molecular compound are used. As low molecular weight compounds, polyacene compounds such as pentacene and tetracene (for example, see Patent Documents 1 to 3) and phthalocyanine compounds such as copper phthalocyanine (for example, refer to Patent Documents 4 and 5) have been proposed.
However, in the case of a low molecular weight compound, it is necessary to repeat the manufacturing process using the same vacuum system as that of silicon, and the problem in the manufacturing process has not been solved.

  Examples of the polymer compound include aromatic compounds such as sexithiophene (for example, see Patent Document 6), polymer compounds such as polythiophene, polythienylene vinylene, and poly (p-phenylene vinylene) (for example, Patent Documents 7 to 7). 10, Non-Patent Document 1).

Such a polymer compound is highly soluble and is advantageous in the manufacturing process because it can be formed by a low-cost technique such as spin coating or dip coating, but has a problem of low carrier mobility. . In addition, since poly (p-phenylene vinylene) is heat-treated after spin-coating a soluble precursor, there is a problem that defects tend to occur in the main chain conjugated polymer and the electrical properties are remarkably lowered.
JP-A-5-55568 JP-A-10-270712 JP 2001-94107 A Japanese Patent Laid-Open No. 5-190877 JP 2000-174277 A JP-A-8-264805 JP-A-8-228034 JP-A-8-228035 Japanese Patent Laid-Open No. 10-125924 Japanese Patent Laid-Open No. 10-190001 Appl. Phys. Lett. , Vol. 73, 108 (1998)

  An object of the present invention is to solve the above problems. That is, an organic semiconductor transistor element that is excellent in solubility and compatibility with a solvent and a resin, uses a charge-transporting polyether or charge-transporting polyester having high carrier mobility, has a high operation speed, and is easy to manufacture. It is an object to provide a method and a semiconductor device using the organic semiconductor transistor element.

〔一般式（ＡＩ−１）および（ＡＩ−２）中、Ａｒは置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、または、置換もしくは未置換の１価の複素環を表し、Ｔは炭素数１〜６の２価の直鎖状炭化水素基または炭素数２〜１０の２価の分枝鎖状炭化水素基を表し、ｍは０〜３の整数を表す。また、Ｘは、下記一般式（ＡＩＩ）で表される置換基を表す。〕

〔一般式（ＡＩＩ）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、およびＲ_６は、置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、置換もしくは未置換の１価の複素環、炭素数１〜１８の１価の直鎖状炭化水素基、又は、炭素数３〜１０の１価の分枝鎖状炭化水素基を表し、ｎは１〜１０の整数を表す。〕 The above-mentioned subject is achieved by the following present invention. That is, the present invention
<1>
An organic including at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field In a semiconductor transistor element,
A charge transporting polyether composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (AI-1) and (AI-2) as a partial structure: It is an organic semiconductor transistor element characterized by containing 1 or more types.

[In the general formulas (AI-1) and (AI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and m represents an integer of 0 to 3. X represents a substituent represented by the following general formula (AII). ]

[In General Formula (AII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted monovalent benzene rings, substituted or unsubstituted aromatic rings 2 to 10 Monovalent polynuclear aromatic hydrocarbon, substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted monovalent heterocyclic ring, monovalent having 1 to 18 carbon atoms Represents a straight-chain hydrocarbon group or a monovalent branched hydrocarbon group having 3 to 10 carbon atoms, and n represents an integer of 1 to 10. ]

〔一般式（ＡＩＩＩ）において、Ａ_１は前記一般式（ＡＩ−１）および（ＡＩ−２）で示される構造から選択された少なくとも１種以上を表し、ｐは５〜５０００の整数を表す。〕 <2>
The organic semiconductor transistor element according to <1>, wherein the organic semiconductor is a charge transporting polyether represented by the following general formula (AIII).

[In General Formula (AIII), A ₁ represents at least one selected from the structures represented by General Formulas (AI-1) and (AI-2), and p represents an integer of 5 to 5000. ]

〔一般式（ＡＩ−１）および（ＡＩ−２）中、Ａｒは置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、または、置換もしくは未置換の１価の複素環を表し、Ｔは炭素数１〜６の２価の直鎖状炭化水素基または炭素数２〜１０の２価の分枝鎖状炭化水素基を表し、ｍは０〜３の整数を表す。また、Ｘは、下記一般式（ＡＩＩ）で表される置換基を表す。〕

〔一般式（ＡＩＩ）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、およびＲ_６は、置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、置換もしくは未置換の１価の複素環、炭素数１〜１８の１価の直鎖状炭化水素基、又は、炭素数３〜１０の１価の分枝鎖状炭化水素基を表し、ｎは１〜１０の整数を表す。〕 <3>
Comprising at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field; A charge transporting polyether composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (AI-1) and (AI-2) as a partial structure: A method for producing an organic semiconductor transistor element comprising producing an organic semiconductor transistor element containing at least one kind by using a solution containing at least one kind of the charge transporting polyether dissolved in a solvent,
The organic semiconductor is formed using a method of applying an external stimulus to the solution and discharging the solution in a droplet form from a nozzle.

[In the general formulas (AI-1) and (AI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and m represents an integer of 0 to 3. X represents a substituent represented by the following general formula (AII). ]

[In General Formula (AII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted monovalent benzene rings, substituted or unsubstituted aromatic rings 2 to 10 Monovalent polynuclear aromatic hydrocarbon, substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted monovalent heterocyclic ring, monovalent having 1 to 18 carbon atoms Represents a straight-chain hydrocarbon group or a monovalent branched hydrocarbon group having 3 to 10 carbon atoms, and n represents an integer of 1 to 10. ]

<4>
<3> The method for producing an organic semiconductor transistor element according to <3>, wherein the external stimulus is pressure.

<5>
Using a solution containing at least one kind of the charge transporting polyether dissolved in a solvent, a coating film forming step for forming a coating film containing the solvent, and a drying step for drying the coating film The method for producing an organic semiconductor transistor element according to <3>, wherein the organic semiconductor transistor element is produced by passing through at least an environment where the oxygen concentration is 100 ppm or less and the water concentration is 100 ppm or less. This is a method for manufacturing an organic semiconductor transistor element.

〔一般式（ＡＩ−１）および（ＡＩ−２）中、Ａｒは置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、または、置換もしくは未置換の１価の複素環を表し、Ｔは炭素数１〜６の２価の直鎖状炭化水素基または炭素数２〜１０の２価の分枝鎖状炭化水素基を表し、ｍは０〜３の整数を表す。また、Ｘは、下記一般式（ＡＩＩ）で表される置換基を表す。〕

〔一般式（ＡＩＩ）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、およびＲ_６は、置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、置換もしくは未置換の１価の複素環、炭素数１〜１８の１価の直鎖状炭化水素基、又は、炭素数３〜１０の１価の分枝鎖状炭化水素基を表し、ｎは１〜１０の整数を表す。〕 <6>
A substrate, and one or more organic semiconductor transistor elements provided on the substrate,
The organic semiconductor transistor element has a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and is insulated from the organic semiconductor and can apply an electric field. A repeating unit comprising at least a gate electrode, wherein the organic semiconductor includes at least one selected from the structures represented by the following general formulas (AI-1) and (AI-2) as a partial structure: A semiconductor device comprising at least one charge transporting polyether.

[In the general formulas (AI-1) and (AI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and m represents an integer of 0 to 3. X represents a substituent represented by the following general formula (AII). ]

[In General Formula (AII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted monovalent benzene rings, substituted or unsubstituted aromatic rings 2 to 10 Monovalent polynuclear aromatic hydrocarbon, substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted monovalent heterocyclic ring, monovalent having 1 to 18 carbon atoms Represents a straight-chain hydrocarbon group or a monovalent branched hydrocarbon group having 3 to 10 carbon atoms, and n represents an integer of 1 to 10. ]

〔一般式（ＢＩ−１）および（ＢＩ−２）中、Ａｒは置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、または、置換もしくは未置換の１価の複素環を表し、Ｔは炭素数１〜６の２価の直鎖状炭化水素基または炭素数２〜１０の２価の分枝鎖状炭化水素基を表し、ｋ、ｌはそれぞれ独立に０または１を表す。また、Ｘは、下記一般式（ＢＩＩ）で表される置換基を表す。〕

〔一般式（ＢＩＩ）中、Ｒ_１、Ｒ_２は、水素原子、アルキル基、置換もしくは未置換のアリール基、又は、置換もしくは未置換のアラルキル基を表し、ｎは１〜１０の整数を表す。〕 <7>
An organic including at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field In a semiconductor transistor element,
1 is a charge transporting polyester composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (BI-1) and (BI-2) as a partial structure. It is an organic semiconductor transistor element characterized by containing at least seeds.

[In the general formulas (BI-1) and (BI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k and l each independently represents 0 or 1. X represents a substituent represented by the following general formula (BII). ]

[In General Formula (BII), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and n represents an integer of 1 to 10. . ]

〔一般式（ＢＩＩＩ−１）および（ＢＩＩＩ−２）中、Ａは上記一般式（ＢＩ−１）および（ＢＩ−２）で示される構造から選択される少なくとも１種を表し、Ｙは２価の炭化水素基を表し、Ｚは２価の炭化水素基を表す。また、Ｒは水素原子、アルキル基、置換もしくは未置換のアリール基、又は、置換もしくは未置換のアラルキル基、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素を表し、Ｂ及びＢ’は−Ｏ−（Ｙ−Ｏ）ｍ−Ｈ、または−Ｏ−（Ｙ−Ｏ）ｍ−ＣＯ−Ｚ−ＣＯ−ＯＲ’を表し、Ｒ’は水素原子、アルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のアラルキル基を表す。ｍは１〜５の整数を表す。ｐは５〜５，０００の整数を表す。〕 <8>
<7> The organic semiconductor transistor element according to <7>, wherein the organic semiconductor is a charge transporting polyester represented by the following general formula (BIII-1) or (BIII-2).

[In General Formulas (BIII-1) and (BIII-2), A represents at least one selected from the structures represented by General Formulas (BI-1) and (BI-2), and Y represents a divalent group. Z represents a divalent hydrocarbon group. R is a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted Alternatively, it represents an unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, and B and B ′ are —O— (YO) m—H, or —O— (YO) m—. CO-Z-CO-OR ', wherein R' represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. m represents an integer of 1 to 5. p represents an integer of 5 to 5,000. ]

〔一般式（ＢＩ−１）および（ＢＩ−２）中、Ａｒは置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、または、置換もしくは未置換の１価の複素環を表し、Ｔは炭素数１〜６の２価の直鎖状炭化水素基または炭素数２〜１０の２価の分枝鎖状炭化水素基を表し、ｋ、ｌはそれぞれ独立に０または１を表す。また、Ｘは、下記一般式（ＢＩＩ）で表される置換基を表す。〕

〔一般式（ＢＩＩ）中、Ｒ_１、Ｒ_２は、水素原子、アルキル基、置換もしくは未置換のアリール基、又は、置換もしくは未置換のアラルキル基を表し、ｎは１〜１０の整数を表す。〕 <9>
Comprising at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field; 1 is a charge transporting polyester composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (BI-1) and (BI-2) as a partial structure. A method for producing an organic semiconductor transistor element comprising producing an organic semiconductor transistor element containing at least one species using a solution containing at least one kind of the charge transporting polyester dissolved in a solvent,
The method of manufacturing an organic semiconductor transistor element, wherein the organic semiconductor is formed using a method in which an external stimulus is applied to the solution and the solution is ejected in a droplet form from a nozzle.

[In the general formulas (BI-1) and (BI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k and l each independently represents 0 or 1. X represents a substituent represented by the following general formula (BII). ]

[In General Formula (BII), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and n represents an integer of 1 to 10. . ]

<10>
<9> The method for producing an organic semiconductor transistor element according to <9>, wherein the external stimulus is pressure.

<11>
Using a solution containing at least one kind of the charge transporting polyester dissolved in a solvent, at least a coating film forming step for forming a coating film containing the solvent and a drying step for drying the coating film The organic semiconductor transistor element manufacturing method according to <9>, wherein the organic semiconductor transistor element is manufactured by passing through an environment where the oxygen concentration is 100 ppm or less and the water concentration is 100 ppm or less. A method for producing an organic semiconductor transistor element, wherein the method is implemented.

〔一般式（ＢＩ−１）および（ＢＩ−２）中、Ａｒは置換もしくは未置換の１価のベンゼン環、置換もしくは未置換の芳香環数２〜１０の１価の多核芳香族炭化水素、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香族炭化水素、または、置換もしくは未置換の１価の複素環を表し、Ｔは炭素数１〜６の２価の直鎖状炭化水素基または炭素数２〜１０の２価の分枝鎖状炭化水素基を表し、ｋ、ｌはそれぞれ独立に０または１を表す。また、Ｘは、下記一般式（ＢＩＩ）で表される置換基を表す。〕

〔一般式（ＢＩＩ）中、Ｒ_１、Ｒ_２は、水素原子、アルキル基、置換もしくは未置換のアリール基、又は、置換もしくは未置換のアラルキル基を表し、ｎは１〜１０の整数を表す。〕 <12>
A substrate, and one or more organic semiconductor transistor elements provided on the substrate,
The organic semiconductor transistor element has a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and is insulated from the organic semiconductor and can apply an electric field. A repeating unit comprising at least a gate electrode, wherein the organic semiconductor includes at least one selected from the structures represented by the following general formulas (BI-1) and (BI-2) as a partial structure: A semiconductor device comprising at least one charge transporting polyester.

[In the general formulas (BI-1) and (BI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k and l each independently represents 0 or 1. X represents a substituent represented by the following general formula (BII). ]

[In General Formula (BII), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and n represents an integer of 1 to 10. . ]

  As described above, according to the present invention, a charge transporting polyether or charge transporting polyester having excellent solubility and compatibility with solvents and resins, high carrier mobility, high operating speed, and production It is possible to provide an organic semiconductor transistor element and a method for manufacturing the same, and a semiconductor device using the organic semiconductor transistor element.

  In the following, the present invention will be described by dividing it into an organic semiconductor transistor element using a charge transporting polyether and an organic semiconductor transistor element using a charge transporting polyester, and then the matters common to both will be described.

-Organic semiconductor transistor device using charge transporting polyether-
The organic semiconductor transistor element of the present invention includes a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and an electric field insulated from the organic semiconductor and applying an electric field. An organic semiconductor transistor element including at least a possible gate electrode, wherein the organic semiconductor is at least one selected from the structures represented by the following general formulas (AI-1) and (AI-2): It is characterized by containing one or more charge transporting polyethers composed of repeating units included as a partial structure.
This charge transporting polyether is excellent in thermal stability during operation, solubility in solvents and resins and phase solubility, and has high carrier mobility. Further, the organic semiconductor transistor element of the present invention has the charge transporting property. Since it has an organic semiconductor containing a polyether, the operation speed is high and the production is easy.

Ar is a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted monovalent condensed ring having 2 to 10 aromatic rings Represents an aromatic hydrocarbon or a substituted or unsubstituted monovalent heterocyclic ring, and T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched chain having 2 to 10 carbon atoms. Represents a hydrocarbon group, and m represents an integer of 0 to 3.
X represents a substituent represented by the following general formula (AII).

In general formula (AII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted monovalent benzene rings, substituted or unsubstituted aromatic rings having 2 to 10 Monovalent polynuclear aromatic hydrocarbon, substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted monovalent heterocyclic ring, monovalent monovalent ring having 1 to 18 carbon atoms A linear hydrocarbon group or a monovalent branched hydrocarbon group having 3 to 10 carbon atoms is represented, and n represents an integer of 1 to 10.

A polynuclear aromatic selected as a structure representing Ar, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ in the general formulas (AI-1), (AI-2), and (AII) The hydrocarbon and the condensed polycyclic aromatic hydrocarbon are not particularly limited. In the present invention, the polynuclear aromatic hydrocarbon and the condensed aromatic hydrocarbon mean specifically defined as follows.
That is, “polynuclear aromatic hydrocarbon” refers to a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present and the rings are bonded by a carbon-carbon bond, and the rings are vinylene. And those bonded via an ethynylene group. Specific examples include biphenyl and terphenyl.
The “condensed aromatic hydrocarbon” represents a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present and the rings share a pair of carbon atoms. Specific examples include naphthalene, anthracene, phenanthrene, pyrene, and fluorene.

In addition, the number of atoms (Nr) constituting the ring skeleton of the heterocyclic ring is preferably Nr = 5 and / or 6. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not particularly limited. For example, a sulfur atom, a nitrogen atom, an oxygen atom and the like are preferably used, and two types are included in the ring skeleton. The above and / or two or more different atoms may be contained. In particular, as a heterocyclic ring having a 5-membered ring structure, thiophene, pyrrole and furan, or a heterocyclic ring in which the 3- and 4-position carbons of the compound are replaced with nitrogen are preferably used. Pyridine is preferably used.
The “polynuclear aromatic hydrocarbon” and the “condensed aromatic hydrocarbon” include a hydrocarbon group in which at least one of the aromatic rings constituting the hydrocarbon group is substituted with a heterocyclic ring.
For example, polynuclear aromatic hydrocarbons in which a part of the aromatic ring is substituted with a heterocyclic ring include those in which at least one of the aromatic rings constituting the biphenyl group is replaced with a heterocyclic ring such as thiophene, or a terphenyl group And those in which at least one benzene ring is replaced with a heterocyclic ring such as thiophene. In addition, examples of the condensed aromatic hydrocarbon in which at least one or more of the aromatic rings are substituted with a heterocyclic ring include carbazole.
Examples of the alkyl group include an alkyl group having 1 to 5 carbon atoms.

Ar, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may have a benzene ring, polynuclear aromatic hydrocarbon, condensed polycyclic aromatic hydrocarbon or heterocyclic substituent as a hydrogen atom, alkyl Group, alkoxy group, aryl group, aralkyl group, substituted amino group, halogen atom, cyano group and the like.
As an alkyl group, a C1-C10 thing is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned. As an alkoxyl group, a C1-C10 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned. As the aryl group, those having 6 to 20 carbon atoms are preferable, and examples thereof include a phenyl group and toluyl group. As the aralkyl group, those having 7 to 20 carbon atoms are preferable, and examples thereof include benzyl group and phenethyl group. Is mentioned. Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, an aralkyl group, and the like, and specific examples are as described above.

  In addition, when X is conjugated with fluorene and thiophene, the interaction between the functional groups of X is strengthened, so that planarity can be improved and electrical characteristics can be improved. Also, in terms of synthesis, fluorene and thiophene can use many synthetic methods such as Suzuki coupling, homocoupling, etc., can be easily reacted, and can obtain a high-purity target product.

  T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms. It is selected from a linear hydrocarbon group and a divalent branched hydrocarbon group having 3 to 7 carbon atoms. A specific structure is shown below.

  Next, specific examples of the structure represented by the general formula (AI-1) are shown in Tables 1 to 26, and specific examples of the structure represented by the general formula (AI-2) are shown in Tables 27 to 50. In addition, in Tables 1-50, the value of m is not specifically limited, Any of 0-3 may be sufficient.

  Examples of the charge transporting polyether comprising a repeating unit having at least one selected from the structures represented by the general formulas (AI-1) and (AI-2) as a partial structure include those represented by the following general formula (AIII): Preferably used.

In the general formula (AIII), A ₁ represents at least one selected from the structures represented by the general formulas (AI-1) and (AI-2), and two or more types of structures A are included in one polymer. ₁ may be included. In general formula (AIII), p represents an integer of 5 to 5000.

The weight average molecular weight Mw of the charge transporting polyether comprising a repeating unit having at least one selected from the structures represented by the general formulas (AI-1) and (AI-2) used in the present invention as a partial structure is 5000 to 5000. Those in the range of 300,000 are preferred.
Specific examples of the above charge transporting polyether represented by the general formula (AIII) are shown in Tables 51 to 53, but the present invention is not limited to these specific examples. In Tables 51 to 53, the numbers in the column “A ₁ ” are structural numbers (specifications of Tables 1 to 50) that are specific examples of the structures represented by the general formulas (AI-1) and (AI-2). Corresponding to the compound numbered in the “Structure” column. Moreover, m in the table means m in the general formulas (AI-1) and (AI-2). Hereinafter, specific examples (compounds) given respective numbers, for example, specific examples given numbers 615 are referred to as display compounds (615).

The said polyether of this invention can be easily manufactured by condensing the compound which has a hydroxyl group shown by the following general formula (AIV) between molecules. Here, _{A 1} is the following formula (AIV) is the same as _{A 1} in the general formula (AIII).

Specifically, the polyether can be synthesized, for example, as follows.
1) The above-mentioned polyether is synthesized by a method in which a compound having two hydroxyalkyl groups in the general formula (AIV) (hereinafter abbreviated as “monomer”) is heated and dehydrated and condensed. Can do. In this case, it is desirable that the monomer be heated and melted without a solvent and reacted under reduced pressure in order to accelerate the polymerization reaction due to the elimination of water. When a solvent is used, a solvent that azeotropes with water, for example, trichloroethane, toluene, chlorobenzene, dichlorobenzene, nitrobenzene, 1-chloronaphthalene, etc. is effective for removing water. 1 to 100 equivalents, preferably 2 to 50 equivalents. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization. If the polymerization does not proceed, the solvent may be removed from the reaction system and heated and stirred in a viscous state.

  2) The polyether can also be synthesized by a dehydration condensation method using a protonic acid such as p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid, or a Lewis acid such as zinc chloride as an acid catalyst. In this case, the acid catalyst is used in the range of 1 to 1/10000 to 1/10 equivalent, preferably 1/1000 to 1/50 equivalent, per equivalent of monomer. In order to remove water generated during the polymerization, it is preferable to use a solvent azeotropic with water. As the solvent, toluene, chlorobenzene, dichlorobenzene, nitrobenzene, 1-chloronaphthalene and the like are effective, and 1 to 100 equivalents, preferably 2 to 50 equivalents, are used with respect to 1 equivalent of the monomer. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization.

  3) The above monomers include alkyl isocyanates such as cyclohexyl isocyanate, alkyl isocyanates such as cyclohexyl cyanide, cyanate esters such as p-tolyl cyanate and 2,2-bis (4-cyanatophenyl) propane, and dichloromethane. It can also be synthesized by a method using a condensing agent such as hexylcarbodiimide (DCC) or trichloroacetonitrile. In this case, the condensing agent is used in a range of 1/2 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 equivalent of the monomer. As the solvent, toluene, chlorobenzene, dichlorobenzene, 1-chloronaphthalene and the like are effective, and 1 to 100 equivalents, preferably 2 to 50 equivalents, are used with respect to 1 equivalent of the monomer. Although reaction temperature can be set arbitrarily, it is preferable to make it react from the room temperature to the boiling point of a solvent. Of the synthesis methods 1), 2) and 3), the synthesis method 1) or 3) is preferred because isomerization and side reactions are unlikely to occur. In particular, the synthesis method 3) is more preferable because the reaction conditions are milder.

  If the solvent is not used after completion of the reaction, it is dissolved in a soluble solvent. In the case of using a solvent, after dropping it in a poor solvent in which alcohols such as methanol and ethanol and non-conjugated polymers such as acetone are difficult to dissolve, the polyether is separated and the polyether is separated. Wash thoroughly with water or organic solvent and dry. Further, if necessary, the reprecipitation treatment in which the monomer is precipitated by dissolving in an appropriate organic solvent and dropping in a poor solvent may be repeated. The reprecipitation treatment is preferably carried out with efficient stirring using a mechanical stirrer or the like. The solvent for dissolving the polyether in the reprecipitation treatment is used in the range of 1 to 100 equivalents, preferably 2 to 50 equivalents, per 1 equivalent of the polyether. The poor solvent is used in an amount of 1 to 1000 equivalents, preferably 10 to 500 equivalents, per 1 equivalent of polyether. Furthermore, in the above reaction, a copolymer can be synthesized by using two or more monomers, preferably 2 to 5, more preferably 2 to 3 monomers. By copolymerizing different types of monomers, electrical characteristics, film formability, solubility, and fluorescence characteristics can be controlled.

If the degree of polymerization of the polyether is too low, the film formability is poor, and it is difficult to obtain a strong film. If the degree of polymerization is too high, the solubility in the solvent is lowered and the processability is deteriorated, so p is 5 to 5000. It is set to a range, preferably 10 to 3000, more preferably 15 to 1000.
In addition, the terminal of the polymer may be a hydroxyl group as in the case of the monomer, that is, the terminal group may be a hydrogen atom. However, if the polymer physical properties such as solubility, film-forming property, and mobility are affected, the terminal group is modified. The physical properties can be controlled. For example, the terminal hydroxyl group can be alkyl etherified with alkyl sulfate, alkyl iodide or the like. The specific reagent can be arbitrarily selected from dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl iodide and the like, and is used in the range of 1 to 3 equivalents, preferably 1 to 2 equivalents with respect to the terminal hydroxyl group. . In this case, a base catalyst can be used, but the base catalyst can be arbitrarily selected from sodium hydroxide, potassium hydroxide, sodium hydride, sodium metal, etc., and is preferably ˜3 equivalents with respect to the terminal hydroxyl group, preferably Is used in the range of 1 to 2 equivalents.

The reaction temperature can be from 0 ° C. to the boiling point of the solvent used. In addition, the solvent used at that time is selected from inert solvents such as benzene, toluene, methylene chloride, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone. However, a single solvent or a mixed solvent of 2 to 3 types can be used.
Depending on the reaction, a quaternary ammonium salt such as tetra-n-butylammonium iodide can be used as a phase transfer catalyst. Alternatively, the terminal hydroxyl group can be acylated using an acid halide to convert the terminal group into an acyl group. The acid halide is not particularly limited, and examples thereof include acryloyl chloride, crotonoyl chloride, methacryloyl chloride, n-butyl chloride, 2-furoyl chloride, benzoyl chloride, cyclohexanecarbonyl chloride, enanthyl chloride, phenylacetyl chloride, o -Toluoyl chloride, m-toluoyl chloride, p-toluoyl chloride, etc. are mentioned, It uses in the range of 1-3 equivalent with respect to the hydroxyl group of a terminal, Preferably it is 1-2 equivalent. In this case, a base catalyst can be used, and the base catalyst can be arbitrarily selected from pyridine, dimethylaminopyridine, trimethylamine, triethylamine, etc., and is 1 to 3 equivalents, preferably 1 to 2 equivalents, with respect to the acid chloride. Use within the range. Examples of the solvent used at that time include benzene, toluene, methyl chloride, tetrahydrofuran, and methyl ethyl ketone. The reaction can be carried out from 0 ° C. to the boiling point of the solvent. Preferably, it is performed in the range of 0 ° C to 30 ° C. Furthermore, acylation can also be performed using an acid anhydride such as acetic anhydride. When using a solvent, specifically, an inert solvent such as benzene, toluene or chlorobenzene can be used. The reaction can be carried out from 0 ° C. to the boiling point of the solvent. Preferably, it may be carried out from 40 ° C. to the boiling point of the solvent.

  In addition, a urethane residue (—CONH—R ′) can be introduced at the terminal using monoisocyanate. Specific monoisocyanates include isocyanic acid benzyl ester, isocyanic acid n-butyl ester, isocyanic acid t-butyl ester, isocyanic acid cyclohexyl ester, isocyanic acid 2,6-dimethyl ester, isocyanic acid ethyl ester, isocyanic acid isopropyl ester. Isocyanic acid 2-methoxyphenyl ester, isocyanic acid 4-methoxyphenyl ester, isocyanic acid n-octadecyl ester, isocyanic acid phenyl ester, isocyanic acid i-propyl ester, isocyanic acid m-tolyl ester, isocyanic acid p-tolyl ester, It can be arbitrarily selected from isocyanic acid 1-naphthyl ester and the like, and is used in the range of 1 to 3 equivalents, preferably 1 to 2 equivalents with respect to the terminal hydroxyl group. Examples of solvents used in this case include benzene, toluene, chlorobenzene, dichlorobenzene, methylene chloride, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like. Can do. The reaction temperature can be from 0 ° C. to the boiling point of the solvent used. If the reaction is difficult to proceed, add a metal compound such as dibutyltin (II) dilaurate, tin (II) octylate or lead naphthenate, or a tertiary amine such as triethylamine, trimethylamine, pyridine or dimethylaminopyridine as a catalyst. You can also.

-Organic semiconductor transistor device using charge transporting polyester-
The organic semiconductor transistor element of the present invention includes a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and an electric field insulated from the organic semiconductor and applying an electric field. An organic semiconductor transistor element including at least a possible gate electrode, wherein the organic semiconductor is at least one selected from the structures represented by the following general formulas (BI-1) and (BI-2): It is characterized by containing one or more kinds of charge transporting polyesters composed of repeating units included as a partial structure.
This charge transporting polyester is excellent in thermal stability during operation, solubility in solvents and resins and phase solubility, and has a high carrier mobility. Further, the organic semiconductor transistor element of the present invention comprises the charge transporting polyester. Therefore, the organic semiconductor containing the organic compound has a high operating speed and is easy to manufacture.

In general formulas (BI-1) and (BI-2), Ar is a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, and a substituted group. Or an unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, wherein T is a divalent linear carbonized carbon having 1 to 6 carbon atoms. Represents a hydrogen group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k and l each independently represents 0 or 1;
X represents a substituent represented by the following general formula (BII).

In general formula (BII), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, n represents an integer of 1 to 10, A range of 2 to 8 is preferable.

In the general formulas (BI-1) and (BI-2), the polynuclear aromatic hydrocarbon and the condensed polycyclic aromatic hydrocarbon selected as the structure representing Ar are not particularly limited. In the present invention, the polynuclear aromatic hydrocarbon and the condensed aromatic hydrocarbon mean specifically defined as follows.
That is, “polynuclear aromatic hydrocarbon” refers to a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present and the rings are bonded by a carbon-carbon bond, and the rings are vinylene. And those bonded via an ethynylene group. Specific examples include biphenyl and terphenyl. The “condensed aromatic hydrocarbon” represents a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present and the rings share a pair of carbon atoms. Specific examples include naphthalene, anthracene, phenanthrene, pyrene, and fluorene.

In addition, the number of atoms (Nr) constituting the ring skeleton of the heterocyclic ring is preferably Nr = 5 and / or 6. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not particularly limited. For example, a sulfur atom, a nitrogen atom, an oxygen atom and the like are preferably used, and two types are included in the ring skeleton. The above and / or two or more different atoms may be contained. In particular, as a heterocyclic ring having a 5-membered ring structure, thiophene, pyrrole and furan, or a heterocyclic ring in which the 3- and 4-position carbons of the compound are replaced with nitrogen are preferably used. Pyridine is preferably used.
The “polynuclear aromatic hydrocarbon” and the “condensed aromatic hydrocarbon” include a hydrocarbon group in which at least one of the aromatic rings constituting the hydrocarbon group is substituted with a heterocyclic ring.
For example, polynuclear aromatic hydrocarbons in which a part of the aromatic ring is substituted with a heterocyclic ring include those in which at least one of the aromatic rings constituting the biphenyl group is replaced with a heterocyclic ring such as thiophene, or a terphenyl group And those in which at least one benzene ring is replaced with a heterocyclic ring such as thiophene. In addition, examples of the condensed aromatic hydrocarbon in which at least one or more of the aromatic rings are substituted with a heterocyclic ring include carbazole.
Examples of the alkyl group include an alkyl group having 1 to 5 carbon atoms.

Ar substituents of benzene ring, polynuclear aromatic hydrocarbon, condensed polycyclic aromatic hydrocarbon and heterocyclic ring include hydrogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, substituted amino group, halogen atom, cyano Groups and the like.
As an alkyl group, a C1-C10 thing is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned. As an alkoxyl group, a C1-C10 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned. As the aryl group, those having 6 to 20 carbon atoms are preferable, and examples thereof include a phenyl group and toluyl group, and as the aralkyl group, those having 7 to 20 carbon atoms are preferable, and examples thereof include benzyl group and phenethyl group. In the case where the Ar group is a condensed polycyclic aromatic hydrocarbon, those having a monovalent vinyl group or ethynyl group in the side chain of thiophene are also suitable. Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, an aralkyl group, and the like, and specific examples are as described above.

  In addition, when X is conjugated with fluorene and thiophene, the interaction between the functional groups of X is strengthened, so that planarity can be improved and electrical characteristics can be improved. Also, in terms of synthesis, fluorene and thiophene can use many synthetic methods such as Suzuki coupling, homocoupling, etc., can be easily reacted, and can obtain a high-purity target product.

  T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms. It is selected from a linear hydrocarbon group and a divalent branched hydrocarbon group having 3 to 7 carbon atoms. A specific structure is shown below.

  Next, specific examples of the structure represented by the general formula (BI-1) are shown in Tables 54 to 74, and specific examples of the structure represented by the general formula (BI-2) are shown in Tables 75 to 92. In Tables 75 to 92, “Bu” is an abbreviation for butyl group, “Oct” is an abbreviation for octyl group, and “Hex” is an abbreviation for hexyl group.

  Examples of the charge transporting polyester comprising a repeating unit containing at least one selected from the structures represented by the general formulas (BI-1) and (BI-2) as a partial structure include the following general formulas (BIII-1) and (BIII -2) is preferably used.

In the general formulas (BIII-1) and (BIII-2), A represents at least one selected from the structures represented by the general formulas (BI-1) and (BI-2). Two or more types of structures A may be included.
In general formulas (BIII-1) and (BIII-2), Y represents a divalent hydrocarbon group, and Z represents a divalent hydrocarbon group. R is a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted Alternatively, it represents an unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, and B and B ′ are —O— (YO) m—H, or —O— (YO) m—. CO-Z-CO-OR ', wherein R' represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. m represents an integer of 1 to 5. p represents an integer of 5 to 5,000.
Specific examples of Y and Z include groups selected from the following formulas (BIV-1) to (BIV-7).

In the formula, R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom. A and b each represent an integer of 1 to 10, c and e each represents an integer of 0, 1 or 2, d and f each represents 0 or 1, and V represents the following formula: It means a divalent substituent represented by (BV-1) to (BV-11).

  In formulas (BV-1) to (BV-11), g represents an integer of 1 to 5, and h and i represent an integer of 0 to 5.

  The weight average molecular weight Mw of the charge transporting polyester comprising a repeating unit containing at least one selected from the structures represented by formulas (BI-1) and (BI-2) as a partial structure used in the present invention is 5000 to 5000. A range of 300,000 is preferable.

Specific examples of the charge transporting polyesters represented by the general formulas (BIII-1) and (BIII-2) are shown in Table 93 to Table 97, but the present invention is not limited to these specific examples. Absent. In Table 93 to Table 97, the numbers in the column “A” are structural numbers (specifications of Tables 54 to 92) which are specific examples of the structures represented by the general formulas (BI-1) and (BI-2). Corresponding to the compound numbered in the “Structure” column. M and p mean m and p in formulas (BIII-1) and (BIII-2).
In Tables 93 to 97, an example in which the structure is shown only in the column “Y” means a specific example of the charge transporting polyester of the general formula (BIII-1), and both “Y” and “Z” The example whose structure is shown in the column means a specific example of the charge transporting polyester of the general formula (BIII-2). Hereinafter, specific examples (compounds) given respective numbers, for example, compounds having the number 715 are referred to as “exemplary compounds (715)”.

  The method for synthesizing the charge transporting polyester used in the present invention can be used in combination with known methods depending on the desired structure, and is not particularly limited, but as a specific example, the general formula (BI- A charge transporting polyester comprising a repeating unit containing at least one selected from the structures represented by 1) and (BI-2) as a partial structure is represented by the general formula (BIII-1) or (BIII-2). The case where it is such a polyester will be described in detail below.

  When the charge transporting polyester used in the present invention is a polyester represented by the general formula (BIII-1) or (BIII-2), a monomer represented by the following general formula (BI-3) For example, it can be synthesized by polymerization by a known method described in the 4th edition, Experimental Chemistry Course Vol. 28 (Maruzen, 1992).

In General Formula (BI-3), A represents at least one selected from the structures represented by General Formulas (BI-1) and (BI-2), and A ′ represents a hydroxyl group, a halogen atom, Alternatively, the group represents —O—R ₆ , where R ₆ represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group.
That is, the polyesters represented by the general formulas (BI-1) and (BI-2) can be synthesized as follows.

  1) When A ′ is a hydroxyl group, a dihydric alcohol represented by HO— (Y—O) m—H is mixed with the monomer in an approximately equivalent amount and polymerized using an acid catalyst. As the acid catalyst, those used for usual esterification reaction such as sulfuric acid, toluenesulfonic acid, trifluoroacetic acid and the like can be used, and 1 / 10,000 to 1/10 parts by weight, preferably 1 part by weight of monomer. It is used in the range of 1/1000 to 1/50 parts by weight. In order to remove water generated during polymerization, it is preferable to use a solvent azeotropic with water, and toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and 1 to 100 parts by weight per 1 part by weight of the monomer. It is used in the range of parts by weight, preferably 2 to 50 parts by weight. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization.

  When the solvent is not used after completion of the reaction, it is dissolved in a soluble solvent. When a solvent is used, the reaction solution is dropped as it is in a poor solvent in which alcohols such as methanol and ethanol and polymers such as acetone are difficult to dissolve, to precipitate the polyester, and after separating the polyester, Wash thoroughly with organic solvent and dry. Further, if necessary, the reprecipitation treatment in which the polyester is precipitated by dissolving in an appropriate organic solvent and dropping in a poor solvent may be repeated. The reprecipitation treatment is preferably carried out with efficient stirring with a mechanical stirrer or the like. The solvent for dissolving the polyester during the reprecipitation treatment is used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, with respect to 1 part by weight of the polyester. The poor solvent is used in an amount of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, based on 1 part by weight of the polyester.

  2) When A ′ is halogen, a dihydric alcohol represented by HO— (Y—O) m—H is mixed with the monomer in an equivalent amount and polymerized using an organic basic catalyst such as pyridine or triethylamine. . An organic basic catalyst is used in 1-10 equivalent with respect to 1 equivalent of monomers, Preferably it is 2-5 equivalent. As the solvent, methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 1 part by weight of the monomer. Used. The reaction temperature can be arbitrarily set. After the polymerization, reprecipitation treatment is performed as described above, and purification is performed.

  In the case of dihydric alcohols with high acidity such as bisphenol, an interfacial polymerization method can also be used. That is, it can polymerize by adding a dihydric alcohol to water, adding an equivalent base and dissolving it, and then adding a monomer solution equivalent to the dihydric alcohol with vigorous stirring. In this case, water is used in an amount of 1 to 1,000 parts by weight, preferably 2 to 500 parts by weight, based on 1 part by weight of the dihydric alcohol. As the solvent for dissolving the monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective. The reaction temperature can be arbitrarily set, and in order to promote the reaction, it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt. The phase transfer catalyst is used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 1 part by weight of the monomer.

3) When A ′ is —O—R _6, an excessive amount of a dihydric alcohol represented by HO— (Y—O) _m —H is added to the monomer, an inorganic acid such as sulfuric acid or phosphoric acid, titanium It can be synthesized by transesterification by heating using an alkoxide, acetate or carbonate such as calcium and cobalt, an oxide of zinc or lead as a catalyst. The dihydric alcohol is used in the range of 2 to 100 equivalents, preferably 3 to 50 equivalents, with respect to 1 equivalent of the monomer. The catalyst is used in the range of 1 / 10,000 to 1 part by weight, preferably 1 / 1,000 to 1/2 part by weight, based on 1 part by weight of the monomer. The reaction is carried out at a reaction temperature of 200 to 300 ° C. After the transesterification from the group —O—R ₆ to the group —O— (Y—O) _m —H is completed, HO— (Y—O) _m —H In order to accelerate the polymerization due to elimination, the reaction is preferably carried out under reduced pressure. Also, HO- _(Y-O) with m -H and high boiling point solvent such as azeotropic 1-chloronaphthalene under normal pressure HO- _(Y-O) with the exception of m -H azeotropically reaction It can also be made.

  Further, polyester can be synthesized as follows. In each of the above cases, a compound represented by the following general formula (BI-4) was formed by adding an excess of dihydric alcohols and reacting, and then the compound was represented by the above general formula (BI-3). What is necessary is just to make it react with a bivalent carboxylic acid or a bivalent carboxylic acid halide etc. by the method similar to the above using it instead of a monomer, and, thereby, polyester can be obtained.

In General Formula (BI-4), A represents at least one selected from the structures represented by General Formulas (BI-1) and (BI-2), and Y represents a divalent alcohol residue. M represents an integer of 1 to 5.
Further, any molecule may be introduced into the terminal of the charge transporting polyester. In that case, the following method is mentioned. That is, when A ′ is a hydroxyl group, the terminal-introducing compound monocarboxylic acid can be copolymerized, or the electron transporting compound after the polymerization reaction of the polymer can be charged and reacted for introduction.
When A ′ is halogen, the monoacid chloride of the terminally introduced compound can be copolymerized, or after the polymerization reaction of the polymer, the monoacid chloride of the terminally introduced compound can be charged and reacted for introduction. When A ′ is —O—R ₆ , the monoester of the terminally introduced compound can be copolymerized, or after the polymerization reaction of the polymer, the monoester of the terminally introduced compound can be charged and reacted for introduction.

-Configuration of organic semiconductor transistor element, manufacturing method, etc.-
Next, the structure of the organic semiconductor transistor element of the present invention using the above-described charge transporting polyether or charge transporting polyester will be described in detail with specific examples.
The organic semiconductor transistor element of the present invention includes a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and an electric field insulated from the organic semiconductor and applying an electric field. A possible gate electrode.
Here, the organic semiconductor includes at least one charge transporting polyether or charge transporting polyester described above. In addition, although the shape of the organic semiconductor transistor element of this invention can be made into a desired shape as needed, it is preferable that it is a thin film form.

Hereinafter, the configuration of the organic semiconductor transistor element of the present invention will be described in more detail with reference to the drawings, but is not limited thereto.
1 to 3 are schematic cross-sectional views showing an example of the configuration of the organic semiconductor transistor element of the present invention. Here, FIGS. 1 and 2 show a case where the organic semiconductor transistor element of the present invention has a field effect transistor (Field Effect Transistor) structure. FIG. 3 shows a case where the organic semiconductor transistor element of the present invention has a static induction transistor (StatIc InductIon TransItor) structure.

1 to 3, members having the same functions are denoted by the same reference numerals, 1 being a substrate, 2 being a source electrode, 3 being a drain electrode, 4 being an organic semiconductor layer, 5 being a gate electrode, and 6 being insulating. Represents a layer. Hereinafter, the configuration of the organic semiconductor transistor element of the present invention shown in FIGS.
In the organic semiconductor transistor element of the present invention shown in FIG. 1, a gate electrode 5 and an insulating layer 6 are provided in this order on a substrate 1, and the source electrode 2 and the drain electrode 3 are separated from each other on the insulating layer 6. The organic semiconductor layer 4 is provided so as to cover the source electrode 2 and the drain electrode 3.

In the organic semiconductor transistor element of the present invention shown in FIG. 2, a gate electrode 5 and an insulating layer 6 are provided in this order on a substrate 1, and a source electrode 2 and the source electrode 2 are formed on the insulating layer 6. The organic semiconductor layer 4 is provided so as to cover the surface opposite to the side in contact with the insulating layer 6. Further, the drain electrode 3 is provided on the surface of the organic semiconductor layer 4 opposite to the side on which the insulating layer 6 is provided, at a position separated from the source electrode 2 in the planar direction of the substrate 1.
Further, in the organic semiconductor transistor element of the present invention shown in FIG. 3, a source electrode 2, an organic semiconductor layer 4, and a drain electrode 3 are stacked in this order on a substrate 1, and a plurality of gate electrodes 5 are formed in the organic semiconductor layer 4. (In the example shown in FIG. 3, four gate electrodes 5 are arranged in parallel with the planar direction of the substrate 1 and at equal intervals).

The gate electrode 5 is arranged in a direction perpendicular to the paper surface so as to be parallel to both the source electrode 2 and the drain electrode 3, and the gate electrodes 5 are also provided so as to be parallel to each other. Yes. In FIG. 3, the gate electrode 5 and the organic semiconductor layer 4 are insulated by an insulating layer (not shown) provided at the interface between them.
In the organic semiconductor transistor element as shown in FIGS. 1 to 3, the current flowing between the source electrode 2 and the drain electrode 3 can be controlled by the voltage applied to the gate electrode 5.

  In addition, when producing any electronic device using the organic semiconductor transistor element of the present invention, it is used as a configuration (semiconductor device) in which one or more organic semiconductor transistor elements of the present invention are mounted on a substrate. A desired electronic device can be manufactured by combining this semiconductor device with another element or circuit.

Next, each member which comprises the organic-semiconductor element and semiconductor device of this invention except an organic-semiconductor part is demonstrated in detail.
As an electrode material used for the source electrode, the drain electrode, and the gate electrode, a material capable of efficiently injecting charges is used. Specifically, a metal, a metal oxide, a conductive polymer, or the like is used.
Examples of the metal include magnesium, aluminum, gold, silver, copper, chromium, tantalum, indium, palladium, lithium, calcium, and alloys thereof. Examples of the metal oxide include metal oxide films such as lithium oxide, magnesium oxide, aluminum oxide, indium tin oxide (ITO), tin oxide (NESA), indium oxide, zinc oxide, and indium zinc oxide.

Examples of the conductive polymer include polyaniline, polythiophene, polythiophene derivatives, polypyrrole, polypyridine, and a complex of polyethylenedioxythiophene and polystyrene sulfonic acid.
In addition, if the difference in ionization potential between the material used for the electrode and the above-described polymer compound used for the organic semiconductor (layer) is large, the charge injection characteristics are deteriorated. Therefore, the material used for the drain electrode and / or the source electrode The difference in ionization potential between the ionization potential and the polymer compound used for the organic semiconductor (layer) is preferably within 1.0 eV, more preferably within 0.5 ev. In view of the difference in ionization potential between the electrode and the polymer compound, it is particularly preferable to use Au as the electrode material.

  As a method for forming an electrode, a thin film produced by using a known thin film forming method such as a vapor deposition method or sputtering as the electrode material described above is formed using a known photolithography method or a lift-off method, or an inkjet or the like. Thus, a method of etching into a desired pattern (electrode shape) using a resist or a method of directly transferring an electrode material such as aluminum can be used. When a conductive polymer is used as the electrode material, it may be dissolved in a solvent and patterned by ink jet or the like.

  Insulating members that insulate between each electrode or between the gate electrode and the organic semiconductor (layer) include inorganic substances such as silicon dioxide, silicon nitride, tantalum oxide, aluminum oxide, titanium oxide, polycarbonate resin, polyester resin, methacrylic resin, acrylic Resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, polystyrene styrene resin, polyvinyl acetate resin, styrene butadiene copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer Examples thereof include, but are not limited to, organic insulating polymers such as silicon resin.

  As the substrate, silicon single crystal or glass doped with phosphorus or the like in high concentration, glass resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, police styrene resin, polyvinyl acetate Examples thereof include, but are not limited to, resins, styrene butadiene copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, plastic substrates such as silicone resins, and the like.

  In particular, when the organic semiconductor transistor element of the present invention is used in an electronic circuit used in an electronic device (hereinafter referred to as “flexible electronic device”) that is required to be flexible, such as electronic paper, digital paper, or portable electronic equipment. It is desirable to use a flexible substrate as the substrate. In particular, by using a substrate having a flexural modulus of 1000 MPa or more, more preferably 5000 MPa or more as the substrate, the substrate can be applied to a flexible display element drive circuit or electronic circuit.

  This is because the organic semiconductor transistor element of the present invention has sufficient elasticity that the organic semiconductor portion contains the above-described polymer compound as a main component, and the element is placed on a flexible substrate. This is because even if formed, it can withstand large deformations and repeated deformations and can maintain stable performance. On the other hand, in an inorganic semiconductor transistor element, since the semiconductor portion is made of an inorganic material and lacks elasticity, it is extremely difficult to use it based on such deformation. Further, the process for manufacturing the inorganic semiconductor transistor element has a disadvantage that plastic cannot be used for the substrate because it requires a high temperature. In addition, even in an organic semiconductor transistor element in which the organic semiconductor portion is mainly composed of a low molecular material, since it lacks elasticity like a polymer material, it is difficult to use it assuming such deformation. Or it is inferior in reliability.

  In the present invention, the term “flexible electronic device” refers to [1] a usage state from a flat state, regardless of whether the power is on or off, such as the electronic paper and digital paper described above. It can be bent, bent, bent, or vice versa. [2] The substrate is provided with one or more components on the substrate. [3] means an electronic device that is required to be flexible at least in the substrate portion provided with the organic semiconductor transistor element.

As a method of forming the organic semiconductor portion in a layered manner, it is particularly preferable to use a liquid phase film forming method, for example, spin coating method, casting method, dipping method, die coating method, roll coating method, bar coating method, ink jet method, Each printing method is used, but is not limited thereto.
However, since it is not necessary to form a pattern by etching after coating, the manufacturing process can be simplified, and high productivity can be obtained even when a large number of organic semiconductor transistor elements are formed on a large-area substrate. Is preferably used.
That is, an image forming technique based on ink jet recording used in an ink jet printer can be used for forming an organic semiconductor portion of an organic semiconductor transistor element.

  In this case, instead of ink, a solution containing at least one charge transporting polyether or charge transporting polyester dissolved in a solvent (hereinafter referred to as “inkjet organic semiconductor solution” is used only for ink jet printing). When not limited to ink-jet printing, it may be simply referred to as “organic semiconductor solution”), and the droplet-shaped organic semiconductor solution is ejected from the nozzle of the droplet ejection head to obtain a desired on the substrate. An organic semiconductor having a desired film thickness and shape can be formed at the position.

  In addition, as a droplet discharge head, the same basic configuration and principle as those of a recording head used in an ink jet printer can be used. That is, by applying an external stimulus such as pressure or heat to the organic semiconductor solution, a method of ejecting the organic semiconductor solution for inkjet from the nozzle into droplets (a so-called piezoelectric inkjet method using a piezoelectric element, utilizing a thermal boiling phenomenon) Can be used.

  However, in the production of the organic semiconductor transistor element of the present invention, the external stimulus is more preferably pressure than heat. When the external stimulus is heat, in the inkjet printing process of forming (solidifying) a coating film by volatilization of the solvent of the organic semiconductor solution that has landed on the substrate from ejection of the inkjet organic semiconductor solution from the nozzle, Since the viscosity of the organic semiconductor solution is greatly changed by heat, it may be difficult to control leveling properties and patterning accuracy. In addition to this, charge transporting polyethers or charge transporting polyesters that are inferior in heat resistance cannot be used, and material options may be narrowed.

Moreover, as an apparatus used for manufacturing the organic semiconductor transistor element of the present invention using the inkjet method, in addition to the above-described droplet discharge head, for example, an organic semiconductor transistor element is formed as necessary. A fixing or conveying means for the substrate or the like, or a droplet discharge head scanning means for scanning the droplet discharge head with respect to the substrate plane direction may be provided.
The organic semiconductor solution for inkjet is not particularly limited in composition and physical properties as long as it contains at least a charge transporting polyether or charge transporting polyester and a solvent as described above. The viscosity of the organic semiconductor solution varies depending on the film thickness to be formed, but is preferably in the range of 0.01 to 1000 cps at about 25 ° C., and preferably in the range of 1 to 100 cps.

When the viscosity is less than 0.01 cps, the organic semiconductor solution that has landed on the substrate tends to spread in the plane direction of the substrate, making it difficult to control the film thickness, and patterning accuracy may be degraded. Moreover, when the viscosity exceeds 1000 cps, the viscosity of the organic semiconductor solution for inkjet may be too high, which may cause ejection failure.
In addition, the viscosity of the organic semiconductor solution for inkjet is determined depending on the charge transporting polyether or charge transporting polyester, the content of other additive components added as necessary, the charge transporting polyether or the charge transporting polyester. By controlling the molecular weight and the like, it can be adjusted to a desired value.

The solvent used in the organic semiconductor solution for inkjet is not particularly limited as long as it can dissolve the charge transporting polyether or the charge transporting polyester. For example, an organic solvent such as a hydrocarbon solvent, an ester solvent, Examples include ether solvents, halogen solvents, alcohol solvents, water, and mixed solvents thereof.
Here, examples of the hydrocarbon solvent include toluene, benzene, xylene, hexane, octane, hexadecane, cyclohexane, cyclohexanone, lactone, tetralin, cumene and the like, and examples of the ester solvent include methyl acetate. , Ethyl acetate, isopropyl acetate, amyl acetate, and the like. Examples of the ether solvent include dibutyl ether and dibenzyl ether. Examples of the halogen solvent include 1,1-dichloroethane, 1 -Fluoroethane, 2,2,2-trifluoroethane, 2,2,3,3,3-pentafluoropropane, chloroform, carbon tetrachloride, monochlorobenzene, o-dichlorobenzene, etc., and the alcohol solvent As methanol, ethanol , I- and propyl alcohol.

In addition, when manufacturing an organic semiconductor transistor element using the inkjet method as described above or other liquid phase film forming methods, the organic semiconductor portion uses an organic semiconductor solution and forms a coating film containing a solvent. The coating film is formed by at least a coating film forming process and a drying process of drying the coating film to form a film made of an organic semiconductor.
Here, the drying step is preferably performed in an environment where the oxygen concentration is 100 ppm or less and the water concentration is 100 ppm or less. If the oxygen concentration or water concentration exceeds 100 ppm, oxygen atoms present as oxygen molecules or water molecules in the atmosphere may deteriorate the charge transporting polyether. If the heat treatment temperature during drying is high, this is the case. This is because excessive deterioration is more likely to occur.

  The oxygen concentration is more preferably 50 ppm or less, and further preferably 10 ppm or less. The water concentration is more preferably 50 ppm or less, and further preferably 10 ppm or less.

Further, a protective layer may be provided in order to prevent deterioration of the organic semiconductor transistor element due to moisture or oxygen. Specific examples of the protective layer material include metals such as In, Sn, Pb, Au, Cu, Ag, and Al, metal oxides such as MgO, SiO ₂ , and TiO ₂ , polyethylene resins, polyurea resins, and polyimide resins. Resin. For forming the protective layer, a vacuum deposition method, a sputtering method, a plasma polymerization method, a CVD method, or a coating method can be applied.
As described above, the organic semiconductor transistor element of the present invention has an on / off ratio of about 10 ² to 10 ⁵ by appropriately selecting the type of polymer compound used in the organic semiconductor portion, the structure of the element, and the like. Within the range, it can be adjusted according to the use of the organic semiconductor transistor element.

Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.
(Example A1)
A gold film was formed to a thickness of 100 nm on a glass substrate by vacuum vapor deposition to obtain a gate electrode. Then, the SiO ₂ to form an insulating layer with a film thickness of 300nm by sputtering on the gate electrode, further, by forming a gold film thickness of 150nm through a metal mask as a source electrode and a drain electrode. Note that the distance between the source electrode and the drain electrode is 50 μm.
Thereafter, an organic semiconductor solution obtained by filtering a dichloroethane solution containing 5% by weight of the exemplified compound (A616) through a PTFE filter having a mesh size of 0.1 μm so as to be electrically connected to the source electrode and the drain electrode has a thickness of 0. A 15 μm thin film was formed to produce an organic semiconductor transistor element.
The organic semiconductor thin film is formed by a dip method in a state where the source electrode and the drain electrode face each other in advance and masked with a resist except for a part of the source electrode and the drain electrode in contact with the region. Subsequently, this coating film was formed through a process of drying at 130 ° C. in an inert gas atmosphere having an oxygen concentration of 5 ppm and a water concentration of 5 ppm.

(Example A2)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the exemplified compound (A621) was used instead of the exemplified compound (A616) used in Example A1.

(Example A3)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the exemplified compound (A626) was used instead of the exemplified compound (A616) used in Example A1.

(Example A4)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the exemplified compound (A638) was used instead of the exemplified compound (A616) used in Example A1.

(Example A5)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the exemplified compound (A650) was used instead of the exemplified compound (A616) used in Example A1.

(Example A6)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the exemplified compound (A651) was used instead of the exemplified compound (A616) used in Example A1.

(Example A7)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the exemplified compound (A671) was used instead of the exemplified compound (A616) used in Example A1.

(Example A8)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the exemplified compound (A679) was used instead of the exemplified compound (A616) used in Example A1.

(Example B1)
A gold film was formed to a thickness of 100 nm on a glass substrate by vacuum vapor deposition to obtain a gate electrode. Then, the SiO ₂ to form an insulating layer with a film thickness of 300nm by sputtering on the gate electrode, further, by forming a gold film thickness of 150nm through a metal mask as a source electrode and a drain electrode. Note that the distance between the source electrode and the drain electrode is 50 μm.
Thereafter, an organic semiconductor solution obtained by filtering a dichloroethane solution containing 5% by weight of the exemplary compound (B727) through a PTFE filter having a mesh size of 0.1 μm so as to be electrically connected to the source electrode and the drain electrode has a thickness of 0. A 15 μm thin film was formed to produce an organic semiconductor transistor element.
The organic semiconductor thin film is formed by a dip method in a state where the source electrode and the drain electrode face each other in advance and masked with a resist except for a part of the source electrode and the drain electrode in contact with the region. Subsequently, this coating film was formed through a process of drying at 130 ° C. in an inert gas atmosphere having an oxygen concentration of 5 ppm and a water concentration of 5 ppm.

(Example B2)
An organic semiconductor transistor element was produced in the same manner as in Example B1, except that the exemplified compound (B741) was used instead of the exemplified compound (B727) used in Example B1.

(Example B3)
An organic semiconductor transistor element was produced in the same manner as in Example B1, except that the exemplified compound (B766) was used instead of the exemplified compound (B727) used in Example B1.

(Example B4)
An organic semiconductor transistor element was produced in the same manner as in Example B1, except that the exemplified compound (B768) was used instead of the exemplified compound (B727) used in Example B1.

(Example B5)
An organic semiconductor transistor element was produced in the same manner as in Example B1, except that the exemplified compound (B785) was used instead of the exemplified compound (B727) used in Example B1.

(Example B6)
An organic semiconductor transistor element was produced in the same manner as in Example B1, except that the exemplified compound (B789) was used instead of the exemplified compound (B727) used in Example B1.

(Comparative Example 1)
Example A1 except that the compound represented by the following structural formula (V) was used in place of the exemplified compound (A616) used in Example A1 above, and an organic semiconductor thin film was formed by vapor deposition instead of dipping. In the same manner, an organic semiconductor transistor element was produced.

(Comparative Example 2)
Poly [2-methoxy-5- (2-ethylhexyl) -1,4-phenylenevinylene] is used instead of the exemplified compound (A616) used in Example A1 above, and vapor deposition is used instead of dipping. An organic semiconductor transistor element was produced in the same manner as in Example A1 except that an organic semiconductor thin film was formed.

(Comparative Example 3)
An organic semiconductor transistor element was produced in the same manner as in Example A1, except that the compound represented by the following structural formula (VI) (weight average molecular weight: 64000) was used instead of the exemplified compound (A616) used in Example A1. .

-Evaluation-
The organic semiconductor transistor elements obtained in Examples and Comparative Examples were measured for current-voltage characteristics when a gate voltage was applied using a semiconductor parameter analyzer (manufactured by Agilent Technologies, 4155C), and carrier mobility (linear region) ) And the on / off ratio were calculated.
In addition, the yield of the charge transporting polymer used in place of the exemplified compound in each of the exemplified compounds used in the examples and the comparative examples is determined by HPLC (high performance liquid). Chromatography) and calculated from the peak area.

Table 98 shows the on / off ratio of the organic semiconductor transistor element manufactured as described above together with the carrier mobility and yield of the charge transporting material used for forming the organic compound layer. As can be seen from Table 98, in the organic semiconductor transistor elements shown in any of the examples, the drain-source current flowing between the source electrode, the organic semiconductor layer, and the drain electrode is changed with the change of the voltage applied to the gate electrode (gate voltage). It showed changing switching characteristics and a good on / off ratio.
However, in the comparative example, it was found that the on / off ratio was inferior to that of the device of the example because the carrier mobility of the charge transporting material used for forming the organic semiconductor thin film was low. Further, when forming an organic semiconductor thin film, there is a case where a liquid phase film forming method cannot be used / a vapor phase film forming method must be used.

In Comparative Example 3, evaluation was performed by synthesizing a general formula (BI-1) in which a divalent fluorene group was introduced as an X group, but the general formula (BI-2) and the general formula (AI-1) were evaluated. ), Even when a divalent fluorene group was introduced as the X group in the general formula (AI-2), only characteristics comparable to or lower than those of Comparative Example 3 could be obtained.
Moreover, in general formula (AI-1), general formula (AI-2), general formula (BI-1), and general formula (BI-2), what introduce | transduced thienylene group as X group was synthesize | combined. Although an attempt was made to try the same evaluation as in Examples, the yield during synthesis was extremely low compared to the exemplified compounds used in Examples, and sufficient amounts could not be obtained.
Further, when the X group was thiophene (the following compound), the yield was as low as 10% or less, and purification was difficult, and even when an organic semiconductor transistor element was produced, it could not be evaluated.

It is the schematic block diagram which showed an example of the laminated constitution of the organic-semiconductor transistor element of this invention. It is the schematic block diagram which showed an example of the laminated constitution of the organic-semiconductor transistor element of this invention. It is the schematic block diagram which showed an example of the laminated constitution of the organic-semiconductor transistor element of this invention.

Explanation of symbols

1 Substrate 2 Source electrode 3 Drain electrode 4 Organic semiconductor layer 5 Gate electrode 6 Insulating layer

Claims (12)

An organic including at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field In a semiconductor transistor element,
A charge transporting polyether composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (AI-1) and (AI-2) as a partial structure: An organic semiconductor transistor element containing at least one kind.

[In the general formulas (AI-1) and (AI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and m represents an integer of 0 to 3. X represents a substituent represented by the following general formula (AII). ]

[In General Formula (AII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted monovalent benzene rings, substituted or unsubstituted aromatic rings 2 to 10 Monovalent polynuclear aromatic hydrocarbon, substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted monovalent heterocyclic ring, monovalent having 1 to 18 carbon atoms Represents a straight-chain hydrocarbon group or a monovalent branched hydrocarbon group having 3 to 10 carbon atoms, and n represents an integer of 1 to 10. ] 2. The organic semiconductor transistor element according to claim 1, wherein the organic semiconductor is a charge transporting polyether represented by the following general formula (AIII).

[In General Formula (AIII), A ₁ represents at least one selected from the structures represented by General Formulas (AI-1) and (AI-2), and p represents an integer of 5 to 5000. ] Comprising at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field; A charge transporting polyether composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (AI-1) and (AI-2) as a partial structure: A method for producing an organic semiconductor transistor element comprising producing an organic semiconductor transistor element containing at least one kind by using a solution containing at least one kind of the charge transporting polyether dissolved in a solvent,
The method of manufacturing an organic semiconductor transistor element, wherein the organic semiconductor is formed using a method in which an external stimulus is applied to the solution and the solution is ejected in a droplet form from a nozzle.

[In the general formulas (AI-1) and (AI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and m represents an integer of 0 to 3. X represents a substituent represented by the following general formula (AII). ]

[In General Formula (AII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted monovalent benzene rings, substituted or unsubstituted aromatic rings 2 to 10 Monovalent polynuclear aromatic hydrocarbon, substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted monovalent heterocyclic ring, monovalent having 1 to 18 carbon atoms Represents a straight-chain hydrocarbon group or a monovalent branched hydrocarbon group having 3 to 10 carbon atoms, and n represents an integer of 1 to 10. ]   4. The method of manufacturing an organic semiconductor transistor element according to claim 3, wherein the external stimulus is pressure.   Using a solution containing at least one kind of the charge transporting polyether dissolved in a solvent, a coating film forming step for forming a coating film containing the solvent, and a drying step for drying the coating film The method for producing an organic semiconductor transistor element according to claim 3, wherein the organic semiconductor transistor element is produced by passing through at least an environment in which the drying step has an oxygen concentration of 100 ppm or less and a water concentration of 100 ppm or less. The manufacturing method of the organic-semiconductor transistor element characterized by the above-mentioned. A substrate, and one or more organic semiconductor transistor elements provided on the substrate,
The organic semiconductor transistor element has a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and is insulated from the organic semiconductor and can apply an electric field. A repeating unit comprising at least a gate electrode, wherein the organic semiconductor includes at least one selected from the structures represented by the following general formulas (AI-1) and (AI-2) as a partial structure: A semiconductor device comprising at least one charge transporting polyether.

[In the general formulas (AI-1) and (AI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and m represents an integer of 0 to 3. X represents a substituent represented by the following general formula (AII). ]

[In General Formula (AII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted monovalent benzene rings, substituted or unsubstituted aromatic rings 2 to 10 Monovalent polynuclear aromatic hydrocarbon, substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, substituted or unsubstituted monovalent heterocyclic ring, monovalent having 1 to 18 carbon atoms Represents a straight-chain hydrocarbon group or a monovalent branched hydrocarbon group having 3 to 10 carbon atoms, and n represents an integer of 1 to 10. ] An organic including at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field In a semiconductor transistor element,
1 is a charge transporting polyester composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (BI-1) and (BI-2) as a partial structure. An organic semiconductor transistor element comprising at least a seed.

[In the general formulas (BI-1) and (BI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k and l each independently represents 0 or 1. X represents a substituent represented by the following general formula (BII). ]

[In General Formula (BII), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and n represents an integer of 1 to 10. . ] The organic semiconductor transistor element according to claim 7, wherein the organic semiconductor is a charge transporting polyester represented by the following general formula (BIII-1) or (BIII-2).

[In General Formulas (BIII-1) and (BIII-2), A represents at least one selected from the structures represented by General Formulas (BI-1) and (BI-2), and Y represents a divalent group. Z represents a divalent hydrocarbon group. R is a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted Alternatively, it represents an unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings, and B and B ′ are —O— (YO) m—H, or —O— (YO) m—. CO-Z-CO-OR ', wherein R' represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. m represents an integer of 1 to 5. p represents an integer of 5 to 5,000. ] Comprising at least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field; 1 is a charge transporting polyester composed of a repeating unit in which the organic semiconductor includes at least one selected from the structures represented by the following general formulas (BI-1) and (BI-2) as a partial structure. A method for producing an organic semiconductor transistor element comprising producing an organic semiconductor transistor element containing at least one species using a solution containing at least one kind of the charge transporting polyester dissolved in a solvent,
The method of manufacturing an organic semiconductor transistor element, wherein the organic semiconductor is formed using a method in which an external stimulus is applied to the solution and the solution is ejected in a droplet form from a nozzle.

[In the general formulas (BI-1) and (BI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k and l each independently represents 0 or 1. X represents a substituent represented by the following general formula (BII). ]

[In General Formula (BII), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and n represents an integer of 1 to 10. . ]   The method of manufacturing an organic semiconductor transistor element according to claim 9, wherein the external stimulus is pressure.   Using a solution containing at least one kind of the charge transporting polyester dissolved in a solvent, at least a coating film forming step for forming a coating film containing the solvent and a drying step for drying the coating film The method of manufacturing an organic semiconductor transistor element according to claim 9, wherein the organic semiconductor transistor element is manufactured by passing through an environment in which the drying step has an oxygen concentration of 100 ppm or less and a moisture concentration of 100 ppm or less. A method for producing an organic semiconductor transistor element, wherein the method is implemented. A substrate, and one or more organic semiconductor transistor elements provided on the substrate,
The organic semiconductor transistor element has a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and is insulated from the organic semiconductor and can apply an electric field. A repeating unit comprising at least a gate electrode, wherein the organic semiconductor includes at least one selected from the structures represented by the following general formulas (BI-1) and (BI-2) as a partial structure: A semiconductor device comprising at least one charge transporting polyester.

[In the general formulas (BI-1) and (BI-2), Ar represents a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having 2 to 10 aromatic rings or a substituted or unsubstituted monovalent heterocyclic ring, and T is a divalent linear chain having 1 to 6 carbon atoms. It represents a hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k and l each independently represents 0 or 1. X represents a substituent represented by the following general formula (BII). ]

[In General Formula (BII), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and n represents an integer of 1 to 10. . ]

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