JP2016131215A - Organic thin film transistor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin film transistor having a practical mobility.SOLUTION: An organic thin film transistor comprises: a primer layer between a gate insulator layer and an organic semiconductor layer. The primer layer is composed of (A) an organic silane thin film obtained by coating a composition containing: a) a hydrolytic condensate of an epoxy group-containing trialkoxysilane; b) polyamines; and c) c-1) n-pentanol or c-2) an organic acid of which pKa is in a range of 2.0-6.0 at 25°C, or alcohols having 2-5 carbon atoms, having a perfluoroalkyl group and/or a perfluoro alkylene group.SELECTED DRAWING: None

Description

  The present invention relates to an organic thin film transistor.

In an organic electric device such as an organic thin film transistor, it is known to provide an intermediate layer in order to suppress peeling and deterioration between organic compound layers. For example, a first organic compound layer and a first organic compound layer on the first organic compound layer A second organic compound layer formed on the substrate, an organic material that dissolves in a solvent for forming the second organic compound layer, and a solvent that dissolves a material that forms the first organic compound layer There is known an organic electric device having an intermediate layer formed between the first organic compound layer and the second organic compound layer by a liquid, specifically, the first organic compound In an organic semiconductor transistor element in which the layer is an organic semiconductor layer and the second organic compound layer is an insulating layer, polycarbonate is used as an organic material / solvent combination in the coating solution formed by the intermediate layer. Over DOO / chloroform, polystyrene / cyclohexanone, polyester / cyclopentanone, acrylic resin / monochlorobenzene and the like are exemplified (see Patent Document 1).
In addition, a thin film transistor using an organic material for the insulating layer and the semiconductor active layer prevents the melting and melting of both layers from occurring in the manufacturing process, reduces the gate leakage current, and provides a more efficient gate bias application effect. The substrate, the gate electrode, the insulating layer, the semiconductor layer, the source electrode, the drain electrode, and the protective film are thin film transistors having a stacked structure in this order, and the semiconductor layer and the insulating layer are made of an organic material, and the insulating layer An organic thin film transistor is known in which a thin film of a water-soluble smectite group layered silicate compound is formed between a layer and the semiconductor layer (see Patent Document 2).

JP 2010-45221 A JP 2004-179542 A

However, even if the intermediate layer as described above is provided, satisfactory carrier mobility has not been obtained.
An object of this invention is to provide the organic thin-film transistor which maintains the adhesiveness of a semiconductor layer and an insulating layer, and has practical carrier mobility.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by providing a specific primer layer between the insulating layer and the semiconductor layer, and the present invention is completed. It came.

That is, the present invention
(1) An organic thin film transistor comprising a primer layer between the gate insulating layer and the organic semiconductor layer, wherein the primer layer comprises the following (A).
(A) Organic silane thin film obtained by applying a composition containing the following a), b) and c) a) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
b) polyamines, and c) c-1) n-pentanol, or c-2) an organic acid or perfluoroalkyl group and / or perfluoroalkylene having a pKa in the range of 2.0 to 6.0 at 25 ° C. C2-C5 alcohols having a group

(2) A display device comprising the organic thin film transistor according to (1).
(3) A sensor comprising the organic thin film transistor according to (1).
(4) An electronic tag having the organic thin film transistor according to (1).

  The organic thin film transistor of the present invention maintains the adhesiveness between the organic semiconductor layer and the insulating layer and exhibits practical carrier mobility.

(A) In the organic thin-film transistor of an Example, it is a graph which shows the transistor characteristic of ID-VG when applying the source-drain voltage of Vd = -50V which is a saturation region. (B) It is a graph which shows the transfer characteristic in the organic thin-film transistor of an Example. (C) It is a graph which shows the output characteristic in the organic thin-film transistor of an Example.

<Organic thin film transistor>
The organic thin film transistor of the present invention includes an organic semiconductor layer, a source electrode and a drain electrode that are in contact with the organic semiconductor layer, and a gate electrode that is positioned with respect to the organic semiconductor layer via a gate insulating layer on the substrate. Preferably it is. In the present invention, a primer layer is provided between the gate insulating layer and the semiconductor layer.

[substrate]
Examples of the substrate include a resin substrate or a glass substrate. As resin substrates, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate A substrate made of (TAC), cellulose acetate propionate (CAP) or the like can be exemplified, and among them, a substrate made of polyethylene naphthalate (PEN) or polyimide (PI) is preferable. The shape of the substrate may be any shape such as a film shape, a sheet shape, and a plate shape, but a film shape is particularly preferable.

  The film may be an unstretched film or a stretched film. Moreover, even if it is a single layer film, the laminated film which laminated | stacked two or more layers by means, such as a lamination and a coating, may be sufficient.

  Although the thickness of a board | substrate is not restrict | limited in particular, 1-1000 micrometers is preferable and 3-500 micrometers is more preferable.

[Gate electrode, source electrode, drain electrode]
The material for forming the source electrode, the drain electrode and the gate electrode is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, Tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium , Beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture Magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium / aluminum mixture, etc. are used, especially platinum, gold, silver, copper, aluminum, indium, ITO, carbon, chromium A / gold / chrome laminate is preferred. Alternatively, a known conductive polymer whose conductivity is improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, or the like is also preferably used. Among them, those having low electric resistance at the contact surface with the organic semiconductor layer are preferable.

  As a method for forming an electrode, a method for forming an electrode using a known photolithographic method or a lift-off method, using a conductive thin film formed by a method such as vapor deposition or sputtering using the above as a raw material, or a metal foil such as aluminum or copper A method of etching using a resist by thermal transfer, ink jet, or the like can be given. Alternatively, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from a coating film by lithography or laser ablation. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.

  Metal fine particle dispersions used in such electrodes can be produced in the liquid phase by physical production methods such as gas evaporation, sputtering, and metal vapor synthesis, colloidal methods, and coprecipitation methods. Examples of the chemical production method include reducing metal and producing fine metal particles. Preferably, JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, and JP-A-2000-239853 are preferred. In the gas described in the colloidal method described in JP-A-2001-254185, 2001-53028, 2001-35255, 2000-124157, 2000-123634, etc. It is a fine metal particle dispersion produced by an evaporation method. After forming a layer using these metal fine particle dispersions, the solvent is dried, and further, heat treatment is performed in the range of 100 to 300 ° C., preferably 150 to 200 ° C. Form.

[Insulation layer]
In the present invention, the insulating layer is composed of an organic compound layer. Examples of organic compounds include polyimides, polyamides, polyesters, polyacrylates, photo-curing resins based on radical photopolymerization, photocationic polymerization, or copolymers containing an acrylonitrile component, polyvinylphenol, polyvinyl alcohol, novolac resins, and cyanoethyl. Pullulan or the like can also be used.

  The organic compound layer can be formed by spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, or other patterning methods such as printing or inkjet. A wet process such as the method according to is preferred. The thickness of these insulating films is preferably 50 nm to 3 μm, more preferably 100 nm to 1 μm.

[Primer layer]
The primer layer is made of (A) an organosilane thin film.

(A) Organic silane thin film obtained by applying a composition containing the following a), b) and c) a) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
b) polyamines, and c) c-1) n-pentanol, or c-2) an organic acid or perfluoroalkyl group and / or perfluoroalkylene having a pKa in the range of 2.0 to 6.0 at 25 ° C. C2-C5 alcohols having a group

a) Hydrolysis condensate of epoxy group-containing trialkoxysilane The hydrolysis condensate of epoxy group-containing trialkoxysilane is a polymer or oligomer condensed with epoxy group-containing trialkoxysilane. When the raw material is already a hydrolysis condensate, the product is a product obtained by further hydrolytic condensation of the hydrolysis condensate.
Although solid content concentration, such as a hydrolysis-condensation product of the epoxy group containing trialkoxysilane in a composition, is not restrict | limited in particular, the range of 1-50 mass% is preferable, 1-10 mass% is more preferable, 1.5- The range of 3% by mass is more preferable.
The solid content concentration may be adjusted to a predetermined solid content concentration from the beginning, or may be adjusted to a predetermined solid content concentration by preparing a composition in a thick state and then diluting the composition.

Although there is no restriction | limiting in particular in the manufacturing method of the hydrolysis condensate of an epoxy-group-containing trialkoxysilane, For example, it can manufacture by methods, such as the following manufacturing methods 1 and 2.
[Production method 1]
The epoxy group-containing trialkoxysilane and / or the hydrolysis condensate thereof is mixed with water and polyamines or imidazoles and stirred.

(Epoxy group-containing trialkoxysilane as a raw material and / or its hydrolysis condensate)
The structure of the epoxy group-containing trialkoxysilane used in production method 1 is not particularly limited as long as it is a trialkoxysilane containing an epoxy group in addition to the functional group portion lost by hydrolysis or the like. The compound represented by the following formula (II) can be exemplified.

(In the formula, R ³ represents a hydrocarbon group having an epoxy group or a glycidoxy group, and R ⁴ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms.)

In R ³ , one or more epoxy groups or glycidoxy groups may be contained, preferably 1 to 3, and both epoxy groups and glycidoxy groups may be contained.
Specific examples of the “hydrocarbon group” of the “hydrocarbon group having an epoxy group or glycidoxy group” of R ³ include an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, and an alkynyl group. , An aryl group, an arylalkyl group, an arylalkenyl group, and the like. The number of carbon atoms is preferably in the range of 1 to 30, and more preferably in the range of 1 to 10.

  The “hydrocarbon group” may have an oxygen atom, a nitrogen atom, or a silicon atom.

  As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -Pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group, etc. Examples of the long-chain alkyl group exceeding the above include lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.

  The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  As the cycloalkylalkyl group, a cycloalkylalkyl group having 4 to 20 carbon atoms is preferable. For example, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylethyl group, a cyclooctylethyl group, a cyclo A decylmethyl group, a cyclotetradecylmethyl group, a cyclooctadecylmethyl group, etc. are mentioned.

  As the alkenyl group, a linear or branched alkenyl group having 2 to 10 carbon atoms is preferable, and it is a linear or branched alkenyl group having 2 to 10 carbon atoms having a carbon-carbon double bond at any one or more positions. Meaning, for example, ethenyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propen-2-yl group, 1-buten-1-yl group, 2-butene- 1-yl group, 3-buten-1-yl group, 1-buten-2-yl group, 3-buten-2-yl group, 1-penten-1-yl group, 4-penten-1-yl group, 1-penten-2-yl group, 4-penten-2-yl group, 3-methyl-1-buten-1-yl group, 1-hexen-1-yl group, 5-hexen-1-yl group, 1 -Hepten-1-yl group, 6-hepten-1-yl group, 1-octen-1-y Group, 7-octen-1-yl group, 1,3-butadiene-1-yl group.

  As the cycloalkenyl group, a cycloalkenyl group having 3 to 8 carbon atoms is preferable, which means an alkenyl group having 3 to 8 carbon atoms having a carbon-carbon double bond at one or more positions and having a cyclic portion. For example, 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group and the like can be mentioned. It is done.

As the alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable. For example, ethynyl group, 1-propyn-1-yl group, 2-propyn-1-yl group, 1-butyn-1-yl group, 3- Butyn-1-yl group, 1-pentyn-1-yl group, 4-pentyn-1-yl group, 1-hexyn-1-yl group, 5-hexyn-1-yl group, 1-heptin-1-yl Group, 1-octyn-1-yl group, 7-octyn-1-yl group and the like.
The cycloalkylalkyl group is preferably a group in which a cycloalkyl group having 3 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded, for example, cyclopropylmethyl group, cyclopropylpropyl group, cyclobutylmethyl group, cyclopentyl. Examples thereof include a methyl group, a cyclopentylethyl group, a cyclohexylethyl group, and a cycloheptylmethyl group.

The aryl group means a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, in addition to a fully unsaturated group, a partially saturated group is also included. Specifically, a phenyl group, a naphthyl group, Examples include an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group, and an aryl group having 6 to 10 carbon atoms is preferable.
The arylalkyl group is preferably a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded, such as benzyl group, phenethyl group, 3-phenyl-n-propyl group, 4-phenyl group. -N-butyl group, 5-phenyl-n-pentyl group, 8-phenyl-n-octyl group, naphthylmethyl group and the like can be mentioned.
As the arylalkenyl group, a group in which an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are bonded is preferable. For example, a styryl group, a 3-phenyl-1-propen-1-yl group, a 3- Phenyl-2-propen-1-yl group, 4-phenyl-1-buten-1-yl group, 4-phenyl-3-buten-1-yl group, 5-phenyl-1-penten-1-yl group, Examples include 5-phenyl-4-penten-1-yl group, 8-phenyl-1-octen-1-yl group, 8-phenyl-7-octen-1-yl group, and naphthylethenyl group.

  Examples of the “hydrocarbon group having an oxygen atom” include an oxirane ring (epoxy group) group such as an alkoxyalkyl group, an epoxyalkyl group, and a glycidoxyalkyl group, an acryloxymethyl group, and a methacryloxymethyl group. .

  Here, the alkoxyalkyl group is preferably a group in which an alkoxy group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms are bonded. For example, a methoxymethyl group, 2-methoxyethyl group, 3-ethoxy-n -Propyl group etc. are mentioned.

The “hydrocarbon group having a nitrogen atom” has —NR ′ ₂ (wherein R ′ represents a hydrogen atom, an alkyl group or an aryl group, and each R ′ may be the same as or different from each other). Or a group having —N═CR ″ 2 (wherein R ″ represents a hydrogen atom, an alkyl group or an aryl group, and each R ″ may be the same as or different from each other). Examples of the alkyl group include the same groups as described above, and examples of the aryl group include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.

For example, the group having —NR ′ ₂ includes a —CH ₂ NH ₂ group, a —CH ₂ (CH ₂ ) ₂ NH ₂ group, a —CH ₂ NHCH ₃ group, and the like. -N = Examples of the group having a _{CR '' 2, -CH 2 N} = CHCH 3 _{group, -CH 2 N = C (CH} 3) 2 _{group, -CH 2 CH 2 N = CHCH} 3 group, _-CH 2 N ═CHPh group, —CH ₂ N═C (Ph) CH ₃ group and the like.

The above-mentioned “hydrocarbon group” may have a substituent other than an epoxy group and a glycidoxy group. Specific examples of such a substituent include a halogen atom, an alkyl group, an alkenyl group, and an alkoxy group. And (meth) acryloxy groups.
Here, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the alkyl group and alkenyl group are the same as the above-described alkyl group and alkenyl group.

Examples of the “alkyl group having 1 to 10 carbon atoms” of the “unsubstituted or substituted alkyl group having 1 to 10 carbon atoms” of R ⁴ are the same as the alkyl group in R ³ of formula (II). be able to.
Specific examples of the substituent “having a substituent” include a halogen atom, an alkoxy group, a (meth) acryloxy group, and the like. Specific examples of the halogen atom and alkoxy group include the same specific examples as the halogen atom and alkoxy group exemplified as the substituent other than the epoxy group and glycidoxy group in R ³ .

  Specific examples of the epoxy group-containing trialkoxysilane or its hydrolysis condensate as a raw material include the following compounds, but are not limited thereto. Moreover, these can be used individually by 1 type or in mixture of 2 or more types.

  Of these, glycidoxyalkyltrialkoxysilane or glycidoxyalkenylalkoxysilane is preferable, and specific examples thereof include compounds represented by the following formulae. These can be used individually by 1 type or in mixture of 2 or more types.

  In the glycidoxyalkyltrialkoxysilane represented by the above formula, n is preferably 1 to 22, and more preferably 1 to 3. Examples of the glycidoxyalkyltrialkoxysilane include 3-glycidoxy-n-propyltrimethoxysila, 3-glycidoxy-n-propyltriethoxysilane and the like.

(water)
The amount of water used is not particularly limited as long as the epoxy group-containing trialkoxysilane used and / or its hydrolysis condensate is more than the amount that can be hydrolyzed and condensed to some extent, specifically, the epoxy group containing used. Trialkoxysilane and / or its hydrolysis condensate (however, when the epoxy group-containing trialkoxysilane and its hydrolysis condensate are used in combination, it represents the total of both, and alkoxy other than the epoxy group-containing trialkoxysilane) Also when silane is used in combination, it represents the total of all of them.) 0.5 mol or more is preferable with respect to 1 mol, 1.0 mol or more, 2.0 mol or more, 5.0 mol or more, or 10 Mole or more is more preferable.

(Polyamines)
The polyamine used is not particularly limited as long as it is a compound having two or more amino groups or imino groups bonded to one or more hydrogen atoms in one molecule. Specifically, ethylenediamine, trimethylenediamine, Tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, methylaminopropylamine, ethylaminopropylamine, N, N′-dimethylhexamethylenediamine, bis (2-methylaminoethyl) ) Ether, menthanediamine, isophoronediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4-aminocyclohexyl) methane, o -Phenylenediamine , M-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylenediamine and the like. These may be used alone or in combination of two or more. it can. Among these, polyalkylene polyamines are preferable, and specific examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and dipropylenetriamine.

  The amount of the polyamine used is not particularly limited, but is 1 / (on the total nitrogen atoms in one molecule of the polyamines with respect to 1 mol of the epoxy group in the epoxy group-containing trialkoxysilane and / or its hydrolysis condensate. The total number of hydrogen atoms) is preferably at least mol, and the range is 1.2 times to 10 times the mole of 1 / (number of total hydrogen atoms on all nitrogen atoms in one molecule of the polyamine), 1.5 times to 5 times. A double mole or a range of 1.8 to 2.5 moles is preferred. When less than 1 / (total number of hydrogen atoms on all nitrogen atoms in one molecule of polyamine) is less than 1 mol, curing may be insufficient and a film with high hardness may not be obtained. 1 / (polyamines 1 When it is larger than 10 times the mole of all hydrogen atoms on all nitrogen atoms in the molecule, polyamines may remain and a film having sufficient hardness may not be obtained.

(Imidazoles)
Specific examples of imidazoles used in the present invention include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2- Heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole , 1- Anoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- (2'-undecylimidazolyl-)-ethyl-s-triazine, 2,4-diamino-6 -[2'-Ethyl-4-imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric Acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzyl Examples thereof include imidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, and the like. These may be used alone or in combination of two or more. Can be used.
The amount of imidazole to be used is not particularly limited as long as it is a catalyst amount or more, and is preferably in the range of 0.001 to 1.0 mol with respect to 1 mol of the epoxy group contained in the trialkoxysilane used. The range of -0.5 mol or 0.01-0.1 mol is more preferable.

(solvent)
In the production method 1, an organic solvent can be used as necessary. The solvent is not particularly limited as long as it can maintain the uniformity and stability of the solution to some extent, and specifically, methanol. , Ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, n-pentanol, isopentanol, s-pentanol, t-pentanol, neopentanol, ethylene glycol, Alcohols such as diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-acetoxyethanol; tetrahydrofuran, ethylene glycol di Ethers such as chill ether, propylene glycol dimethyl ether and tetrahydropyran; Ketones such as acetone, methyl ethyl ketone and acetylacetone; Esters such as methyl acetate and ethylene glycol monoacetate; Formamide, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as pyrrolidone and N-methylpyrrolidone, among which alcohol having 1 to 5 carbon atoms is preferable. These can be used alone or in combination of two or more. The alcohol having 1 to 5 carbon atoms may have a substituent such as a halogen atom on an appropriate carbon. Specific examples of such alcohol include perfluoroethanol and perfluoropentanol. can do.
These can be used individually by 1 type or in mixture of 2 or more types. In consideration of the working environment and the reduction of the residue on the coating film, alcohols having 3 or less carbon atoms are preferable, and isopropanol, n-propanol and the like can be particularly preferably exemplified. In consideration of the storage stability of the hydrolyzed condensate, it is preferable to use n-pentanol.
As the other solvent, water is preferably used. In that case, the organic solvent to be used is preferably an organic solvent that is soluble in water. In addition, the ratio of water to the organic solvent is preferably an amount ratio that makes a uniform solution after using a necessary amount. When an organic solvent that dissolves relatively well in water such as alcohol having 3 or less carbon atoms is used, the mass ratio of water to organic solvent (water / organic solvent) is preferably in the range of 30/70 to 95/5. , 50/50 to 90/10, 60/40 to 80/20, or 65/35 to 75/25 are more preferable.
In addition, when an organic solvent that is relatively difficult to dissolve in water such as alcohol having 4 or more carbon atoms is used, the amount of water used for hydrolysis of trialkoxysilane is low because the solubility of water in the organic solvent is low. It is preferable to use it in an amount in a range where the solution becomes uniform more than the necessary amount.
The amount of the solvent to be used is not particularly limited, but the appearance of the coating film using the composition containing the hydrolysis condensate, the coating property and curability of the composition, the properties of the coating film using the composition, the composition In consideration of the storage stability of the product or the hydrolysis-condensation product, it is preferable to use an amount such that the solid content concentration in the reaction solution is in the range of 0.5 to 50% by mass, The range of 1.0-20 mass%, 1.0-10 mass%, 1.5-5.0 mass%, or 1.8-3 mass% is further more preferable.

(Production conditions)
Mixing and stirring an epoxy group-containing trialkoxysilane and / or its hydrolysis condensate, water, and a polyamine having two or more amino groups or imino groups in which one or more hydrogen atoms are bonded in one molecule, and an organic solvent Thus, it is preferable to produce a hydrolysis-condensation product of an epoxy group-containing trialkoxysilane, but the mixing order and stirring speed are not particularly limited, and any order or any speed can be set. In this case, an acid can be added as necessary. Specific examples of the acid to be added include organic acids and mineral acids. More specifically, examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p -Examples of mineral acids such as toluenesulfonic acid and methanesulfonic acid include hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, and the like. Among them, pKa at 20 ° C is 2.0 to 6.0. It is preferred to use a range of organic acids. Specific examples of such organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isocaproic acid, chloroacetic acid, fluoroacetic acid, bromoacetic acid, and 3-chloropropion. Acid, 2-bromopropionic acid, 2-hydroxybutyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyanoacetic acid, oxalic acid, malonic acid, 2,2-dimethylmalonic acid, adipic acid, succinic acid Pimelic acid, phthalic acid, glutaric acid, oxaloacetic acid, citric acid, isocitric acid, cyclohexane-1,1-dicarboxylic acid, tartaric acid, o-, m-, p-anisic acid, benzoic acid, o-chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-, m-, p-nitrobenzoic acid, m-, p-aminobenzoic acid, sa Tyric acid, phthalic acid, ilophthalic acid, trans-cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, glucholic acid, crotonic acid, lactic acid, 2-hydroxy-2-methylpropionic acid, pyruvic acid, mandelic acid, malic acid , Levulinic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid and the like. The amount of the acid to be used is not particularly limited, but is preferably in the range of 0.3 to 1.2 mol, 0.5 to 1.0 mol, or 0.6 with respect to 1 mol of the polyamine or imidazole to be used. A range of ˜0.9 mol is more preferable. When the amount is less than 0.3 mol, the storage stability of the composition may be lowered. When the amount is more than 1.2 mol, a coating film having sufficient hardness may not be formed.
The temperature at the time of mixing and stirring is not particularly limited, and it is preferably in the range of room temperature to the boiling point of the solvent used, more preferably at room temperature. In this case, the room temperature is the outside air temperature at the place where mixing and stirring is performed, but a temperature in the range of 15 to 35 ° C is preferable.
At room temperature, the epoxy group-containing trialkoxysilane, water, and a polyamine having two or more amino groups or imino groups in which one or more hydrogen atoms are bonded in one molecule or all imidazoles coexist. It is preferable to stir for 2 to 3 hours.
After hydrolysis, if necessary, dilute with an organic solvent or water.
Although the solid content concentration of the composition containing the obtained hydrolysis condensate is not particularly limited, it is preferably used in the range of 0.5 to 50% by mass, 1.0 to 30% by mass, 1.0 to The range of 20 mass%, 1.0-10 mass%, 1.5-5.0 mass%, or 1.8-3.0 mass% is more preferable. If it is less than 0.5% by mass, it may be difficult to form a film uniformly, and if it is more than 50% by mass, the stability of the composition, the transparency of the coating film, the appearance, or There may be a problem in coating properties. The solid content concentration may be adjusted to a predetermined solid content concentration from the beginning, or may be adjusted to a predetermined solid content concentration by preparing a composition in a thick state and then diluting the composition.
As other components, tetraalkoxysilanes, trialkoxysilanes other than epoxy group-containing trialkoxysilane, or dialkoxysilanes can be appropriately added to the above-described epoxy group-containing trialkoxysilane.
Specific examples of such alkoxysilanes include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (isopropoxy) silane, and tetra (n-butoxy) silane; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane , N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyl Riethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3, 3, 3 -Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltriethoxysilane , Tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane Toxisilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meta ) Atacryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriiso Trialkoxysilanes such as propoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane , Di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldi Ethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di- -Octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, heptadecafluorodecylmethyl Examples include dialkoxysilanes such as dimethoxysilane, and these partially hydrolyzed condensates can also be used.
Specific examples of such a partial hydrolysis-condensation product include trade names “MKC silicate MS51”, “MKC silicate MS56”, “MKC silicate MS57”, and “MKC silicate MS60” manufactured by Mitsubishi Chemical Corporation (both are tetramethoxy). Silane condensate); trade names “Ethyl silicate 40” and “ethyl silicate 48” (both are condensates of tetraethoxysilane) manufactured by Colcoat Co., Ltd. As specific examples of the alkoxysilane condensate, trade names “MKC silicate MS56B15”, “MKC silicate MS56B30”, “MKC silicate MS58B15”, “MKC silicate MS56I30”, “MKC silicate MS56F20” manufactured by Mitsubishi Chemical Corporation; Product name of It can be exemplified MS-485 ", and the like.

[Production method 2]
Water and, if necessary, a silanol condensation catalyst are added to the epoxy group-containing trialkoxysilane and / or its hydrolysis condensate, and the temperature is 5 to 100 ° C., preferably 20 to 60 ° C., 1 minute to 10 days, preferably 30 React for 24 minutes.

As the raw material epoxy group-containing trialkoxysilane and / or its hydrolysis condensate, the same ones as shown in production method 1 can be used. Further, in the same manner as described in production method 1, trialkoxysilane, dialkoxysilane other than tetraalkoxysilane, epoxy group-containing trialkoxysilane and / or its hydrolysis condensate, or a partial hydrolysis condensate thereof coexist. It can also be manufactured.
The amount of water is not particularly limited as long as the epoxy group-containing trialkoxysilane used and / or the hydrolysis condensate thereof is an amount that can be hydrolyzed to some extent, and specifically, the trialkoxysilane used and / or Or 0.5 mol or more is preferable with respect to 1 mol of the hydrolysis-condensation products, 1.0 mol or more, 2.0 mol or more, 5.0 mol or more, or 10 mol or more is more preferable.
The amount of the silanol condensation catalyst used is not particularly limited, but the molar amount relative to the amount of trialkoxysilyl group converted as uncondensed in the raw material epoxy group-containing trialkoxysilane and / or its hydrolysis condensate. The ratio (silanol catalyst / silyl group) is preferably in the range of 0.001 to 1.0, more preferably in the range of 0.01 to 1.0, or 0.1 to 0.5.

A silanol condensation catalyst can be used individually by 1 type or in combination of 2 or more types.
In the composition of the present invention, polyamines or imidazoles are used as the curing agent or curing accelerator of the epoxy group-containing trialkoxysilane, and therefore it is preferable to use polyamines and imidazoles as the silanol condensation catalyst. Details of the polyamines and imidazoles are as described above in the production method of the present invention.

    The z-average particle diameter measured by the dynamic light scattering method of the hydrolysis-condensation product of the epoxy group-containing trialkoxysilane used in the present invention is 5 from the viewpoint of film hardness, coating unevenness during coating, etc. The range of ˜50 nm is preferable, and 5 to 30 nm is more preferable. If it is larger than 50 nm, the pot life is short, there is a problem in storage stability, and smear may occur after coating. If it is smaller than 5 nm, the hardness of the coating film obtained from this composition is It may be insufficient.

b) Polyamines As polyamines, the polyamines shown in the above production method 1 can be exemplified. The amount used is also as described in the production method 1.
c) c-2) Organic acid having a pKa in the range of 2.0 to 6.0 at 25 ° C. The organic acid used in the composition for forming the organic silane thin film has a pKa at 25 ° C. of 2.0 to 6. It is not particularly limited as long as it is an organic acid in the range of 0, preferably in the range of 3.0 to 5.0. Specifically, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isoyoshichi Herbic acid, caproic acid, isocaproic acid, chloroacetic acid, fluoroacetic acid, bromoacetic acid, 3-chloropropionic acid, 2-bromopropionic acid, 2-hydroxybutyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyano Acetic acid, oxalic acid, malonic acid, 2,2-dimethylmalonic acid, adipic acid, succinic acid, pimelic acid, phthalic acid, glutaric acid, oxaloacetic acid, citric acid, isocitric acid, cyclohexa 1,1-dicarboxylic acid, tartaric acid, o-, m-, p-anisic acid, benzoic acid, o-chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-, m- , P-nitrobenzoic acid, m-, p-aminobenzoic acid, salicylic acid, phthalic acid, ilophthalic acid, trans-cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, glucholic acid, crotonic acid, lactic acid, 2-hydroxy -2-Methylpropionic acid, pyruvic acid, mandelic acid, malic acid, levulinic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid and the like can be exemplified, among which aliphatic monocarboxylic acid, or substituted or unsubstituted Benzoic acid can be preferably exemplified.
The amount of the acid to be used is not particularly limited, but is preferably in the range of 0.3 to 1.2 mol, 0.5 to 1.0 mol, or 0.6 to 0.00 mol per mol of the polyamine to be used. A range of 9 moles is more preferred.
When the amount is less than 0.3 mol, the storage stability of the composition may be lowered. When the amount is more than 1.2 mol, a coating film having sufficient hardness may not be formed.
c) c-2) C2-C5 alcohol having a perfluoroalkyl group and / or a perfluoroalkylene group A perfluoroalkyl group and / or a perfluoroalkylene group used in a composition for forming an organic silane thin film Specific examples of the alcohol having 2 to 5 carbon atoms include trifluoromethanol, 2,2,2-trifluoroethanol, 1,1,2,2,2-pentafluoroethanol, 3,3,3 -Trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,2,2,3,3,3-heptafluoro-1-propanol, 1,1, 1,3,3,3-hexafluoro-2-propanol, 2-trifluoromethyl-2-propanol, 2-methyl-1,1,1,3,3,3-hexaph Fluoro-2-propanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, nonafluoro-t-butanol, 2,2,3,3,4,4,5,5-octa Examples thereof include fluoro-1-pentanol.
The amount of fluoroalcohol used in the composition is not particularly limited, but is preferably 30% by mass or more, and more preferably 40% by mass or more of the entire composition. When it is less than 30% by mass, the long-term storage stability of the composition may be lowered.

(Other ingredients that can be included in the composition)
The composition for forming an organic silane thin film can use an organic solvent in order to adjust the solid content concentration in the composition, and as such a solvent, a solvent that can maintain the uniformity and stability of the solution. Specific examples include, but are not limited to, methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, n-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene Alcohols such as glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether; tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran Ethers such as acetone, methyl ethyl ketone, acetylacetone, etc .; esters such as methyl acetate, ethylene glycol monoacetate; formamide, N, N-dimethylformamide, N, N-dimethylacetamide, pyrrolidone, N-methylpyrrolidone, etc. Examples include amides, and alcohols having 1 to 5 carbon atoms are preferable. These can be used alone or in combination of two or more.
It is preferable to use water as the other solvent. In that case, the organic solvent to be used is preferably an organic solvent that dissolves in water. In addition, the ratio of water to the organic solvent is not particularly limited as long as it is an amount ratio that makes a uniform solution as a composition after using a necessary amount. When an organic solvent that dissolves relatively well in water such as alcohol having 3 or less carbon atoms is used, the mass ratio of water to organic solvent (water / organic solvent) is preferably in the range of 30/70 to 95/5. , 50/50 to 90/10, 60/40 to 80/20, or 65/35 to 75/25 are more preferable.
In addition, when an organic solvent that is relatively difficult to dissolve in water such as alcohol having 4 or more carbon atoms is used, the amount of water used for hydrolysis of trialkoxysilane is low because the solubility of water in the organic solvent is low. It is preferable to use it in an amount in a range where the composition becomes more than the necessary amount.
Depending on the application, other components can be added to the composition for forming an organic silane thin film. Specifically, inorganic fine particles such as colloidal silica and colloidal alumina, various surfactants, and dyes. And pigments, dispersion materials, water repellent materials, thickeners, fragrances, antibacterial components, and the like.

(Mixing ratio)
The solid content concentration in the composition for forming the organic silane thin film is not particularly limited, but it is 0 in consideration of the appearance of the coating film, coating properties, curability, properties of the coating film, storage stability of the composition, and the like. It is preferable to use an amount in the range of 5 to 50% by mass, 1.0 to 30% by mass, 1.0 to 20% by mass, 1.0 to 10% by mass, 1.5 to 5.0% by mass. Or in the range of 1.8 to 3% by mass. If it is less than 0.5% by mass, it may be difficult to form a film uniformly, and if it is more than 50% by mass, the stability of the composition, the transparency of the coating film, the appearance, or There may be a problem in coating properties.
The amount of the organic solvent and water used can be determined as appropriate in consideration of the amount of the fluoroalcohol used in combination as long as the solid content concentration can be adjusted.

(Production conditions for the composition)
Although the manufacturing method in particular of the composition for organic silane thin film formation is not restrict | limited, Specifically, the following methods etc. can be illustrated.
i) An epoxy group-containing trialkoxysilane and / or a hydrolysis condensate thereof, a silanol condensation catalyst, water and, if necessary, an organic solvent (including n-pentanol) are mixed and stirred at room temperature, and then polyamines, If necessary, an organic acid or a fluoroalcohol is added and diluted with an organic solvent (including n-pentanol) and water as necessary.
ii) Epoxy group-containing trialkoxysilane and / or hydrolysis condensate thereof, water, organic solvent (including n-pentanol) and polyamines are mixed and stirred at room temperature, and further an organic acid or fluoroalcohol as necessary Are further diluted with an organic solvent (including n-pentanol) and water as necessary.
iii) Mixing epoxy group-containing trialkoxysilane and / or hydrolysis condensate thereof, water, alcohol as a solvent (including n-pentanol), polyamines, organic acid or fluoroalcohol as necessary at room temperature, Stir and further dilute with an organic solvent (including n-pentanol) and water as needed.
iv) An epoxy group-containing trialkoxysilane, water, an alcohol (including n-pentanol) as a solvent, a polyamine, and an organic acid or fluoroalcohol as necessary are mixed and stirred at room temperature.
The stirring temperature is not particularly limited, but is preferably in the range of room temperature to the boiling temperature of the solvent used, and more preferably performed at room temperature. In this case, the room temperature is the outside temperature of the place where stirring is performed, but a range of 15 to 35 ° C. is preferable.

(Formation method of organosilane thin film)
The composition for forming an organic silane thin film forms a coating film on the surface of the target insulating layer or organic semiconductor layer by any known coating means such as brush, spray, dipping, spin coating, bar coating, and gravure printing. be able to. Drying can be performed by room temperature drying and / or heating. Specifically, it is carried out at 20 ° C. to 250 ° C., preferably 20 ° C. to 150 ° C. for 10 seconds to 24 hours, preferably 30 seconds to 10 hours.
The thickness of the thin film to be obtained is not particularly limited, but is preferably more than 10 nm and 5 μm or less.

  The primer layer has the above configuration. Therefore, in the organic thin film transistor, the affinity between the insulating layer and the organic semiconductor layer is improved, and the leakage current can be suppressed. Organic thin film transistors have practical carrier mobility.

[Organic semiconductor layer]
As a material of the organic semiconductor layer constituting the organic thin film transistor, a π-conjugated material is used, for example, polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole), poly (3,4-disubstituted pyrrole). Polypyrroles such as: polythiophene, poly (3-substituted thiophene), poly (3,4-disubstituted thiophene), polythiophenes such as polybenzothiophene, polyisothianaphthenes such as polyisothianaphthene, polychenylene vinylene Such as polychenylene vinylenes; poly (p-phenylene vinylenes) such as poly (p-phenylene vinylene), polyaniline, poly (N-substituted aniline), poly (3-substituted aniline), poly (2,3- Substituted anilines) and the like, polyacetylenes such as polyacetylene; Polydiacetylenes such as lenene, polyazulenes such as polyazulene, polypyrenes such as polypyrene, polycarbazoles such as polycarbazole and poly (N-substituted carbazole), polyselenophenes such as polyselenophene; polyfuran, polybenzofuran, etc. Poly (p-phenylene) s such as poly (p-phenylene); polyindoles such as polyindole; polypyridazines such as polypyridazine; naphthacene, pentacene, hexacene, heptacene, dibenzopentacene, tetrabenzopentacene , Pyrene, dibenzopyrene, chrysene, perylene, coronene, terylene, ovarene, quaterylene, circaanthracene and other polyacenes; a part of carbon of polyacenes such as N, S and O atoms, carbonyl group Derivatives substituted with functional groups such as triphenodioxazine, triphenodithiazine, hexacene-6,15-quinone, etc .; polymers such as polyvinylcarbazole, polyphenylene sulfide, polyvinylene sulfide; JP-A-11-195790 The polycyclic condensates described in 1) can be used.

  Further, for example, α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (α, which is a thiophene hexamer having the same repeating unit as those polymers. Oligomers such as 3-butoxypropyl) -α-sexithiophene and styrylbenzene derivatives can also be preferably used.

  Furthermore, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in JP-A-11-251601; naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4-trifluoromethyl) Benzyl) naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (1H, 1H-perfluorooctyl), N, N′-bis (1H, 1H-perfluorobutyl) and N, N '-Dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diimide derivative, naphthalene 2,3,6,7 tetracarboxylic acid diimide and other naphthalene tetracarboxylic acid diimides, and anthracene 2,3,6,7-tetra Condensed ring tet such as anthracene tetracarboxylic acid diimides such as carboxylic acid diimide Carboxylic acid diimides; C60, C70, C76, C78, C84 etc. fullerenes; carbon nanotubes such as SWNT, merocyanine dyes, etc. dyes such hemicyanine dyes and the like.

  Among these π-conjugated materials, thiophene, vinylene, chelenylene vinylene, phenylene vinylene, p-phenylene, a substituent thereof, or two or more of these are used as a repeating unit, and the number n of the repeating units is 4 to 4 At least 1 selected from the group consisting of an oligomer of 10 or a polymer in which the number n of repeating units is 20 or more, a condensed polycyclic aromatic compound such as pentacene, fullerenes, condensed ring tetracarboxylic diimides, and metal phthalocyanine Species are preferred.

  Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex. Organic molecular complexes such as can also be used. Furthermore, (sigma) conjugated polymers, such as polysilane and polygermane, and organic-inorganic hybrid material as described in Unexamined-Japanese-Patent No. 2000-260999 can also be used.

  The organic semiconductor layer can be produced by vacuum deposition, molecular beam epitaxial growth, ion cluster beam method, low energy ion beam method, ion plating method, CVD method, sputtering method, plasma polymerization method, electrolytic polymerization method, chemical polymerization method, etc. Examples of the method include a combination method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a die coating method, and an LB method. However, among these, in terms of productivity, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, or a method capable of easily and precisely forming a thin film using an organic semiconductor solution, or A casting method or the like is preferable. Furthermore, a gap casting method or an edge casting method, which is a special casting method, is preferable for controlling the orientation of the molecular compound constituting the organic semiconductor layer.

  In addition, as described in Advanced Material 1999 No. 6, p. 480 to 483, a precursor such as pentacene is soluble in a solvent, a target organic material formed by heat treatment of a precursor film formed by coating A thin film may be formed.

  Although there is no restriction | limiting in particular as a film thickness of an organic-semiconductor layer, The characteristic of the obtained element is largely influenced by the film thickness of the active layer which consists of organic semiconductors, and the film thickness changes with organic semiconductors. Is preferably 1 μm or less, particularly preferably 10 to 300 nm.

[Dopant layer]
The organic thin film transistor of the present invention includes a dopant layer between the source and drain electrodes and the organic semiconductor layer. Examples of the dopant layer include materials having functional groups such as acrylic acid, acetamide, dimethylamino group, cyano group, carboxyl group, and nitro group, benzoquinone derivatives, tetracyanoethylene and tetracyanoquinodimethane, and derivatives thereof. Materials that accept electrons, such as materials having functional groups such as amino, triphenyl, alkyl, hydroxyl, alkoxy, and phenyl groups, substituted amines such as phenylenediamine, anthracene, benzo Even if it contains a material that becomes a donor as an electron donor, such as anthracene, substituted benzoanthracenes, pyrene, substituted pyrene, carbazole and its derivative, tetrathiafulvalene and its derivative, etc. Good.

The doping means introducing an electron-donating molecule (acceptor) or an electron-donating molecule (donor) into the thin film as a dopant. Accordingly, the doped thin film is a thin film containing the condensed polycyclic aromatic compound and the dopant. A well-known thing can be employ | adopted as a dopant used for this invention.
Examples of the material used for the dopant layer further include ferric chloride, TCNQ, F4TCNQ, fullerene and derivatives thereof, and F4TCNQ is preferable.

[Self-assembled monolayer]
In addition, a self-assembled monolayer (SAM) is provided between the primer layer and the organic semiconductor layer in order to increase the charge mobility of the organic semiconductor layer. Specifically, as the component for forming SAM, octadecyltrichlorosilane, octadecyltrimethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane (β-PTS), Examples include trichloromethylsilazane, alkane phosphoric acid, alkane phosphonic acid, alkane sulfonic acid, alkane carboxylic acid and the like.

  The organic thin film transistor of the present invention can be used by being incorporated into various electronic devices. For example, as a drive element that is actively driven in various display devices such as a liquid crystal display device, an organic EL display device, and electronic paper, a transistor element used in various sensors, and a memory together with a capacitor in an electronic tag (IC tag) Can be used as an element.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.
[Production Example 1]
After mixing 2.0 g of 3-glycidoxy-n-propyltrimethoxysilane, 0.5 g of diethylenetriamine, 0.5 g of benzoic acid, 70.0 g of water and 28.0 g of isopropyl alcohol, the mixture was stirred at room temperature for 2 hours. And 3% of coating composition [E-2] was prepared in conversion of the mass concentration of solid content.

[Example 1]
On a glass substrate, using a vacuum vapor deposition machine “EX-400” (vacuum degree: 1.3 × 10 −4 Pa) manufactured by ULVAC, a chromium (Cr) layer having a thickness of 3 nm and a gold (Au) having a thickness of 20 nm. A layer and a chromium (Cr) layer having a thickness of 5 nm were stacked in this order to form a gate electrode.
Next, an insulating layer made of polyimide having a thickness of 455 nm was formed on the gate electrode by spin coating.
Next, on the insulating layer, using a spin coater (2000 rpm), the coating film forming solution [E-2] prepared in Production Example 1 was diluted 2 times with a diluent, applied and dried (warm) for 20 seconds. Air drying, 100 ° C., about 10 minutes) and ultraviolet irradiation (condensing high-pressure mercury lamp, 160 W / cm, lamp height of 9.8 cm, integrated irradiation amount of about 500 mJ / cm 2) gave a primer layer having a thickness of 150 nm. Next, an organic semiconductor layer was formed in accordance with a coating method developed by the present inventors (edge casting: Appl. Phys. Exp. 2, 111501 (2009)). That is, the glass substrate on which the primer layer had been formed was cut into 2.5 × 2.5 cm ² and a piece of silicon substrate for holding a solution (hereinafter also referred to as “solution holding structure”) was placed on the substrate. While tilting the substrate, an organic semiconductor solution (C10-DNBDT, manufactured by Pie Crystal Co., Ltd.) was hung on the edge of the solution holding structure at 120 ° C. The crystal was attached to the substrate while the crystal was growing as the solvent evaporated, and the crystal growth was completed in a few minutes. In this state, the crystal film was completely dried under reduced pressure at 60 ° C. for 8 hours (film thickness: 10 to 100 nm).
In order to produce a source / drain electrode on this organic semiconductor layer, a 1 nm thick dopant layer made of F4TCNQ was formed using a shadow mask of a channel (L: 100 μm, W: 2000 μm), and then gold was deposited to 40 nm. The bottom gate / top contact type organic thin film transistor was fabricated by vapor deposition with a thickness.
About the produced organic thin-film transistor, the transport characteristic was measured using the semiconductor parameter analyzer (model number "keithley 4200", the Keithley Instruments company make).
FIG. 1 (a) shows the result in the saturation region, and FIG. 1 (b) shows the result in the linear region.
From the result of FIG. 1A, the carrier mobility and the threshold voltage in the saturation region were calculated using the following formula (1).

ここで、Ｉ_ｄはドレイン電流、Ｗはチャネルの幅、Ｌはチャネルの長さ、μはキャリア移動度、Ｃ_ＯＸはゲート絶縁膜の単位面積当たりのキャパシタンス、Ｖ_Ｇはゲート電圧、Ｖ_Ｔは閾値電圧である。
ドレイン電圧（ＶＤ）は−５０Ｖとし、ゲート電圧（ＶＧ）を３０Ｖ〜−５０Ｖに変化させて移動度を測定した。飽和領域において１．９ｃｍ^２／Ｖｓのキャリア移動度を得ることができた。閾値電圧は、２．５×１０^−１Ｖであった。
図１（ｂ）の結果から、下記式（２）を用いて、線形領域におけるキャリア移動度及び閾値電圧を算出した。

Here, I _d is the drain current, W is the channel width, L is the channel length, μ is the carrier mobility, C _OX is the capacitance per unit area of the gate insulating film, V _G is the gate voltage, and V _T is It is a threshold voltage.
The drain voltage (VD) was −50 V and the gate voltage (VG) was changed from 30 V to −50 V to measure mobility. A carrier mobility of 1.9 cm ² / Vs could be obtained in the saturation region. The threshold voltage was 2.5 × 10 ⁻¹ V.
From the result of FIG. 1B, the carrier mobility and the threshold voltage in the linear region were calculated using the following formula (2).

ドレイン電圧（ＶＤ）は−１Ｖとし、ゲート電圧（ＶＧ）を３０Ｖ〜−５０Ｖに変化させて移動度を測定した。線形領域では２ｃｍ^２／Ｖｓのキャリア移動度を得ることができた。閾値電圧は、−２３Ｖであった。
図１（ｃ）に有機薄膜トランジスタの出力特性を示す。ドレイン電流（ＩＤ）とゲート電圧（ＶＧ）、ドレイン電流（ＩＤ）とドレイン電圧（ＶＤ）は、いずれも明瞭な相関関係を示し、実施例の有機薄膜トランジスタは、優れた特性を示すことが確認された。

The drain voltage (VD) was set to -1 V, and the mobility was measured by changing the gate voltage (VG) from 30 V to -50 V. A carrier mobility of 2 cm ² / Vs could be obtained in the linear region. The threshold voltage was −23V.
FIG. 1C shows the output characteristics of the organic thin film transistor. The drain current (ID) and the gate voltage (VG), and the drain current (ID) and the drain voltage (VD) all show a clear correlation, and it was confirmed that the organic thin film transistor of the example showed excellent characteristics. It was.

Claims (4)

An organic thin film transistor comprising a primer layer between a gate insulating layer and an organic semiconductor layer, wherein the primer layer comprises the following (A).
(A) Organic silane thin film obtained by applying a composition containing the following a), b) and c) a) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
b) polyamines, and c) c-1) n-pentanol, or c-2) an organic acid or perfluoroalkyl group and / or perfluoroalkylene having a pKa in the range of 2.0 to 6.0 at 25 ° C. C2-C5 alcohols having a group   A display device comprising the organic thin film transistor according to claim 1.   A sensor comprising the organic thin film transistor according to claim 1.   An electronic tag comprising the organic thin film transistor according to claim 1.

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