TW201631041A - Organic thin film transistor - Google Patents

Abstract

An organic thin film transistor including, as a gate insulator film, an isolation layer composed of an organic-inorganic complex thin film containing (a) a condensation product of an organosilicon compound represented by the following formula (I) (wherein, R represents an organic group having a carbon atom directly bonded to Si, X represents a hydroxyl group or a hydrolysable group, n represents 1 or 2, each of R may be the same or different from each other if n is 2, and each of X may be the same or different from each other if (4-n) is 2 or more), and (b) a cured material of an electromagnetic radiation curable compound is provided. RnSiX4-n (I).

Description

Organic thin film transistor

This invention relates to an organic thin film transistor.

The present application claims priority based on Japanese Patent Application No. 2015-005413, filed on Jan.

As an organic insulator having a low threshold voltage and a driving voltage and having a high charge mobility with an organic active layer, an organic inorganic insulator forming composition containing (i) an organic-inorganic hybrid, and (ii) one or more organic metals is known. A compound and/or one or more organic polymers, and (iii) a solvent which dissolves the components (i) and (ii) above (see Patent Document 1). It is known that the organic-inorganic hybrid compound is an organic decane compound or a polymer obtained by hydrolyzing and condensing an organodecane compound in an organic solvent using an acid or a base catalyst and water, and the organometallic compound is titanium (IV) n-butoxide. A titanium compound.

Further, as a novel organic insulator composition having excellent solubility in an organic solvent and a monomer and having a high dielectric constant, an organic insulator composition containing i) an organic/inorganic metal represented by the following formula 1 is known. a mixed substance, ii) a monomer and/or an organic polymer, and iii) a solvent which dissolves the above components i) and ii). It is known that the compound represented by the following formula (1) is an acid or a base. The catalyst and water are obtained by subjecting an organodecane compound and an organometallic compound to a hydrolysis reaction or a polycondensation reaction in an organic solvent (see Patent Document 2).

In the above formula, M is a metal atom, and R ¹ , R ² and R ³ are each independently a (meth)acryloyl group having 2 to 5 carbon atoms, a (meth)acryloxy group or an epoxy group-substituted carbon. The alkyl group having a number of 1 to 10, a vinyl group or the like, and each of R ⁴ , R ⁵ and R ⁶ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-120371

[Patent Document 2] Japanese Patent Laid-Open No. 2006-70029

However, even if an insulating layer is provided using the organic insulator composition as described above, there is still room for improvement in terms of maintaining adhesion to the organic semiconductor layer and having practical carrier mobility.

It is an object of the present invention to provide an organic thin film transistor which maintains adhesion to an organic semiconductor layer and has a practical carrier mobility.

The present inventors have made an effort to solve the above problems, and as a result, have found that the above problems can be solved by providing an organic semiconductor layer on a substrate having a specific insulating layer laminated thereon, and the present invention has been completed.

That is, the present invention encompasses the following aspects.

(1) An organic thin film transistor comprising a gate insulating layer comprising an organic-inorganic composite film comprising the following a) and b), a) a condensate of an organic cerium compound represented by the formula (I), and b) A hardened substance of an electromagnetic radiation curable compound.

R _n SiX _4-n (I)

(wherein R represents a carbon atom directly bonded to an organic group of Si, X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2, and when n is 2, each R may be the same or different, and (4-n) is When 2 or more, each X can be the same or different)

(2) The organic thin film transistor according to the above (1), wherein the organic ruthenium compound represented by the above formula (I) is composed of an organic ruthenium compound Si1 and an organic ruthenium compound Si2, wherein the organic ruthenium compound Si1 is obtained by Fedors The solubility parameter SP1 of R obtained by the push algorithm is smaller than the solubility parameter SP2 of the electromagnetic radiation curable compound obtained by the Fedors algorithm, and the solubility parameter SP1 of the organic germanium compound Si2 is smaller than the solubility parameter SP2. Not up to 1.6 or equal to the above solubility parameter SP2 or larger than the above solubility parameter SP2,

The molar ratio of the above organic cerium compound Si1 to the above organic cerium compound Si2 is Si:Si2 of 5:5 to 10:0.

(3) The organic thin film transistor according to the above (1), wherein the organic oxime compound represented by the above formula (I) is a compound represented by the formula (I-1) and a compound represented by the formula (I-2). And if present, is formed by the hydrolysis condensate, R ¹ _n SiX _4-n . . . (I-1)

(wherein, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ represents a vinyl group-containing hydrocarbon group; and X represents a hydroxyl group or hydrolyzability. Base, they can be the same or different)

R ² _n SiX _4-n . . . (I-2)

(wherein, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² represents an organic group in which a carbon atom is directly bonded to a vinyl group-containing hydrocarbon group of Si in the formula; X represents a hydroxyl group. Or a hydrolyzable group, which may be the same or different from each other, {[a compound of the formula (I-1)] + [if present, a unit derived from a compound of the formula (I-1) in the hydrolysis condensate]} /{[Compound of the formula (I-1)] + [Compound of the formula (I-2)] + [if present, a unit derived from the compound of the formula (I-1) in the hydrolysis condensate] + [if If present, the unit derived from the compound of the formula (I-2) in the hydrolysis condensate]}×100=30-100 mol%, and {[the compound of the formula (I-2)]+[if present, a unit derived from the compound of the formula (I-2) in the hydrolysis condensate]}/{[a compound of the formula (I-1)]+[a compound of the formula (I-2)]+[if present, hydrolysis condensation a unit derived from the compound of the formula (I-1)] + [if present, a unit derived from the compound of the formula (I-2) in the hydrolysis condensate]} × 100 = 0 to 70 mol % .

(4) A display device comprising any one of the above (1) to (3) Organic thin film transistor.

(5) A sensor comprising the organic thin film transistor according to any one of the above (1) to (3).

(6) An electronic label comprising the organic thin film transistor according to any one of the above (1) to (3).

The organic thin film transistor of the present invention maintains adhesion to an organic semiconductor layer and exhibits practical carrier mobility.

Fig. 1A is a view showing the transistor characteristics of I _D - V _G when a source/drain voltage of V _D = -30 V is applied as a saturation region in the organic thin film transistor of Example 1.

Fig. 1B is a view showing the communication characteristics of the organic thin film transistor of Example 1.

Fig. 2A is a graph showing the carrier mobility (field-effect mobility) of the organic thin film transistor of Example 1 with respect to the saturation region of the gate voltage.

Fig. 2B is a graph showing the carrier mobility (effective mobility) with respect to the gate voltage in the linear region.

Fig. 3 is a graph showing the output characteristics of the organic thin film transistor of Example 1.

Fig. 4A is a view showing the transistor characteristics of I _D - V _G when a source/drain voltage of V _D = -30 V is applied as a saturated region in the organic thin film transistor of Example 2.

Fig. 4B is a view showing the communication characteristics of the organic thin film transistor of Example 2.

5A is a view showing a saturated region of the organic thin film transistor of Example 2 with respect to a gate voltage. A map of carrier mobility (field efficiency mobility).

Fig. 5B(b) is a graph showing the carrier mobility (effective mobility) with respect to the gate voltage in the linear region.

Fig. 6 is a graph showing the output characteristics of the organic thin film transistor of Example 2.

<Organic Thin Film Transistor>

The organic thin film transistor of the present invention preferably includes an organic semiconductor layer on the substrate, a source electrode and a drain electrode in contact with the organic semiconductor layer, and a gate electrode provided with an insulating layer interposed therebetween with respect to the organic semiconductor layer. .

[substrate]

A resin substrate is mentioned as a board|substrate. As the resin substrate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether oxime (PES), polyether oxime, polyether ether ketone, polyphenyl sulphate can be exemplified. a substrate composed of polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), etc., wherein polyethylene naphthalate is preferably used. A substrate composed of an ester (PEN) or a polyimine (PI). The shape of the substrate may be any shape such as a film shape, a sheet shape, or a plate shape, and is preferably a film shape.

The substrate may be composed of an unstretched film or may be composed of a stretched film. Further, it may be a single layer film, or a laminated film obtained by laminating two or more layers by lamination or coating.

The thickness of the substrate is not particularly limited, but is preferably 1 to 1000 μm, more preferably 3 to 500 μm.

[gate electrode, source electrode, drain electrode]

The material forming the source electrode, the drain electrode, and the gate electrode is not particularly limited as long as it is a conductive material, and platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, antimony, or indium can be used. , palladium, rhodium, iridium, ruthenium, aluminum, osmium, iridium, molybdenum, tungsten, tin oxide-niobium, indium oxide-tin (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glass graphite, silver paste and carbon Pulp, lithium, barium, sodium, magnesium, potassium, calcium, barium, titanium, manganese, zirconium, gallium, germanium, 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., particularly preferably a laminate of platinum, gold, silver, copper, aluminum, indium, ITO, carbon, chromium/gold/chromium. Alternatively, a known conductive polymer such as conductive polyaniline, conductive polypyrrole, conductive polythiophene, poly(ethylenedioxythiophene), and polystyrenesulfonic acid may be suitably used to increase conductivity by doping or the like. The complex and the like. Among them, it is preferable that the contact surface resistance with the organic semiconductor layer is small.

Examples of the method for forming the electrode include a method in which a conductive film formed by using the above-described raw material by vapor deposition or sputtering is formed into an electrode by a known lithographic method or a lift-off method; A method of etching on a metal foil such as aluminum or copper by using a resist formed by thermal transfer, inkjet, or the like. Further, the solution or the dispersion of the conductive polymer or the conductive fine particle dispersion can be patterned by direct ink jetting, or can be formed by a coating film by lithography or laser ablation. Further, a method of patterning an ink (ink) or a conductive paste containing a conductive polymer or conductive fine particles by a printing method such as relief printing, gravure, lithography or screen printing may be used.

Examples of the method for producing the metal fine particle dispersion liquid used in such an electrode include a physical production method such as a vapor phase evaporation method, a sputtering method, and a metal vapor synthesis method, or a colloid method. The precipitation method is equivalent to a chemical formation method in which a metal ion is reduced in a liquid phase to form a metal fine particle, and is preferably a Japanese Patent Laid-Open No. Hei 11-76800, a Japanese Patent Laid-Open No. Hei 11-80647, and a Japanese Patent Laid-Open No. 11- The colloidal method disclosed in Japanese Laid-Open Patent Publication No. 2000-239853, the Japanese Patent Publication No. 2001-254185, the Japanese Patent Publication No. 2001-53028, and the Japanese Patent Laid-Open No. 2001-35255, A fine metal particle dispersion produced by a vapor phase evaporation method described in Japanese Laid-Open Patent Publication No. 2000-123634, and the like. After the layer is formed by using the metal fine particle dispersion, the solvent is dried, and further heat-treated at 100 to 300 ° C, preferably 150 to 200 ° C, to thermally fuse the metal fine particles, thereby forming an electrode.

[Insulation]

The insulating layer is composed of (A) an organic-inorganic composite film as a gate insulating film.

The organic-inorganic composite film constituting the insulating layer contains at least a condensate of a) an organic cerium compound and b) a cured product of an electromagnetic radiation curable compound.

"a) Condensate of organic bismuth compounds"

The organic hydrazine compound used in the present invention is represented by the following formula (I).

R _n SiX _4-n (I)

In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, and X represents a hydroxyl group or a hydrolyzable group. n represents 1 or 2, and when n is 2, each R may be the same or different, and when (4-n) is 2 or more, each X may be the same or different.

Here, as the R, the "carbon atom is directly bonded to the organic group of Si", A hydrocarbon group which may also be substituted may be mentioned.

The hydrocarbon group of the above-mentioned "hydrocarbon group which may be substituted" is preferably a hydrocarbon group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, and an alkynyl group. , aryl, arylalkyl, arylalkenyl and the like.

Further, the above "hydrocarbon group" may have an oxygen atom, a nitrogen atom or a ruthenium atom.

The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a third group. Butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-decyl, isodecyl, n-decyl and the like. Further, examples of the alkyl group having a long chain of more than 10 carbon atoms include a lauryl group, a thirteen group, a myristyl group, a pentadecyl group, a palmity group, a heptadecyl group, and a stearyl group.

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.

The cycloalkylalkyl group is preferably a cycloalkylalkyl group having 4 to 20 carbon atoms, and examples thereof include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, and a cycloheptyl group. Base, cyclooctylethyl, cyclodecylmethyl, cyclotetrakisylmethyl, cyclooctadecylmethyl, and the like.

The alkenyl group is preferably a linear or branched alkenyl group having 2 to 10 carbon atoms, which means a straight or branched alkene having 2 to 10 carbon atoms having a carbon-carbon double bond at any one or more positions. Examples of the group include a vinyl group, a 1-propen-1-yl group, a 2-propen-1-yl group, a 1-propen-2-yl group, a 1-buten-1-yl group, and a 2-buten-1-yl group. , 3-buten-1-yl, 1-buten-2-yl, 3-buten-2-yl, 1-penten-1-yl, 4-penten-1-yl, 1-pentene -2-yl, 4-penten-2-yl, 3-methyl-1-buten-1-yl, 1-hexen-1-yl, 5-hexen-1-yl, 1-heptene -1-yl, 6-hepten-1-yl, 1-octen-1-yl, 7-octene-1 - group, 1,3-butadien-1-yl and the like.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 8 carbon atoms, which means an alkenyl group having 3 to 8 carbon atoms which has a carbon-carbon double bond and has a cyclic moiety. : 1-cyclopenten-1-yl, 2-cyclopenten-1-yl, 1-cyclohexen-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl Wait.

The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a 1-propyn-1-yl group, a 2-propyn-1-yl group, a 1-butyn-1-yl group, and 3 -butyn-1-yl, 1-pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 5-hexyn-1-yl, 1-heptyne-1 -yl, 1-octyn-1-yl, 7-octyn-1-yl and the like.

The cycloalkylalkyl group is preferably a group in which a cycloalkyl group having 3 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms, and examples thereof include a cyclopropylmethyl group and a cyclopropylpropyl group. , cyclobutylmethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylethyl, cycloheptylmethyl and the like.

The aryl group means a monocyclic or polycyclic aryl group, and in the case of a polycyclic aryl group, in addition to being completely unsaturated, a partially saturated group is also included, and specifically, a phenyl group, a naphthyl group or an anthracene is exemplified. The aryl group, the fluorenyl group, the indanyl group, the tetrahydronaphthyl group and the like are preferably an aryl group having 6 to 10 carbon atoms.

The arylalkyl group is preferably a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a 3-phenyl group. Propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 8-phenyl-n-octyl, naphthylmethyl and the like.

The arylalkenyl group is preferably a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a styryl group and a 3-phenyl-1-propene group. 1-yl, 3-phenyl-2-propen-1-yl, 4-phenyl-1-buten-1-yl, 4-phenyl-3-buten-1-yl, 5-phenyl- 1-penten-1-yl, 5-phenyl-4-pentene-1 -yl, 8-phenyl 1-octene-1-yl, 8-phenyl-7-octene-1-yl, naphthylvinyl and the like.

Examples of the "hydrocarbon group having an oxygen atom" include a group having an oxirane ring (epoxy group) such as an alkoxyalkyl group, an alkylene oxide group or a glycidoxyalkyl group, and an acryloxy group. Base, methacryloxymethyl group, and the like.

Here, the alkoxyalkyl group is preferably a group in which an alkoxy group having 1 to 6 carbon atoms is bonded to an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methoxymethyl group and a 2- Methoxyethyl, 3-ethoxy-n-propyl and the like.

The epoxyalkyl group is preferably a linear or branched alkylene oxide having 3 to 10 carbon atoms, and examples thereof include a glycidyl group, a glycidylmethyl group, and a 2-epoxypropylethyl group. , 3-cyclopropylpropyl, 4-epoxypropylbutyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 5,6-epoxyhexyl, etc. Alkyl group of epoxy group; β-methylepoxypropyl group, β-ethyl epoxypropyl group, β-propyl epoxypropyl group, 2-epoxypropylpropyl group, 2-epoxypropyl group , 3-epoxypropylbutyl, 2-methyl-3-epoxypropylpropyl, 3-methyl-2-epoxypropylpropyl, 3-methyl-3,4-epoxy Branched ring containing butyl, 3-ethyl-3,4-epoxybutyl, 4-methyl-4,5-epoxypentyl, 5-methyl-5,6-epoxyhexyl An alkyl group of an oxy group or the like.

Examples of the glycidoxyalkyl group include a glycidoxymethyl group and a glycidoxypropyl group.

The "hydrocarbon group having a nitrogen atom" preferably has a group of -NR' ₂ (wherein R' represents a hydrogen atom, an alkyl group or an aryl group, and each R' may be the same or different), or has - N=CR" ₂ (wherein R" represents a hydrogen atom, an alkyl group or an aryl group, and each R" may be the same or different from each other. The alkyl group may be the same as the above, and as an aryl group, Examples thereof include a phenyl group, a naphthyl group, an inden-1-yl group, and a phenan-1-yl group.

For example, examples of the group having -NR' ₂ include a -CH ₂ NH ₂ group, a -CH ₂ (CH ₂ ) ₂ NH ₂ group, and a -CH ₂ NHCH ₃ group. Examples of the group having -N=CR" ₂ include: -CH ₂ N=CHCH ₃ group, -C 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.

Examples of the substituent which may be substituted or not include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a methacryloxy group. The alkyl group, the alkenyl group, and the aryl group are the same as those in R.

In the above, from the viewpoint of the inorganication of the surface of the organic-inorganic composite film, a vinyl group, a group having an oxirane ring group, a group having -NR' ₂ or a group having -N=CR" ₂ is Good base.

Further, in the formula (I), n represents 1 or 2, and particularly preferably n = 1. When n is 2, each R may be the same or different. Further, these may be used alone or in combination of two or more.

In the formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) of the formula (I) is 2 or more, each X may be the same or different. The hydrolyzable group means that, for example, it can be hydrolyzed at 25 to 100 ° C in the presence of no catalyst or excess water to form a stanol group, or a oxane condensate can be formed. Specific examples thereof include an alkoxy group, a decyloxy group, a halogen atom, an isocyanate group, an unsubstituted or substituted amino group, and the like, and preferably an alkoxy group having 1 to 4 carbon atoms or A carbon number of 1 to 6 carbon atoms.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third butoxy group. The decyloxy group having 1 to 6 carbon atoms (wherein the carbon number does not include the carbon of the carbonyl group) may, for example, be an ethoxy group or a benzyloxy group. Make Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Further, the condensate of the organic hydrazine compound contained in the (A) organic-inorganic composite film means a further condensate of the condensate of the organic hydrazine compound and/or the condensate of the organic hydrazine compound.

The blending ratio of the condensate of the organic cerium compound is preferably from 2 to 98% by mass, more preferably from 5 to 50% by mass, even more preferably from 5 to 30%, based on the total solid content of the (A) organic-inorganic composite film. quality%.

As a preferred aspect of the organic ruthenium compound used in the present invention, specifically, a mixture of the following a-1), a-2), and a-3) can be exemplified.

A-1) A compound represented by the formula (I-1).

R ¹ _n SiX _4-n . . . (Ii)

In the formula, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ represents a vinyl group-containing hydrocarbon group. X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other. Here, as the organic group or the hydrolyzable group, those described in the formula (I) are preferably exemplified. The vinyl group-containing hydrocarbon group may, for example, be an alkenyl group such as a vinyl group, an allyl group, a 3-butenyl group or a 4-hexenyl group (preferably a C2-C8 alkenyl group).

A-2) A compound represented by the formula (I-2).

R ² _n SiX _4-n . . . (I-2)

In the formula, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² represents an organic group in which a carbon atom is directly bonded to a vinyl group-containing hydrocarbon group of Si in the formula. X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other. Here, examples of the organic group other than the vinyl group-containing hydrocarbon group include those having a vinyl group-containing organic group such as an alkenyl group or an arylalkenyl group removed from the formula (I). The hydrolyzable group can be exemplified by those described in the formula (I).

A-3) if present, the hydrolysis condensate.

The compound represented by the formula (I-2) and the hydrolysis-condensation product contained as a unit may not necessarily exist. The hydrolyzed condensate compound is hydrolyzed and condensed to form a diene-bonded dimer or the like, and may be obtained by hydrolyzing and condensing only the compound of the formula (I-1) or the formula (I-2). The compound of the formula (I-1) and the compound of the formula (I-2) may be hydrolyzed and condensed, or two or more of them may be mixed.

{[Compound of the formula (I-1)] + [if present, a unit derived from the compound of the formula (I-1) in the hydrolysis condensate]} / {[a compound of the formula (I-1)] + [ a compound of the formula (I-2)] + [if present, a unit derived from a compound of the formula (I-1) in the hydrolysis condensate] + [if present, a form derived from the hydrolysis condensate (I- 2) The unit of the compound]} × 100 is preferably 30 to 100 mol%, more preferably 30 to 95 mol%.

On the other hand, {[the compound of the formula (I-2)] + [if present, the unit derived from the compound of the formula (I-2) in the hydrolysis condensate]} / {[formula (I-1)) Compound] + [compound of formula (I-2)] + [unit of compound derived from formula (I-1), if present, in hydrolysis condensate] + [if present, derived from hydrolyzed condensate The unit of the compound of the formula (I-2)]}100 is preferably 0 to 70 mol%, more preferably 5 to 70 mol%.

Further, the average particle diameter of the hydrolysis condensate is preferably from 2 nm to 100 nm, more preferably from 5 nm to 30 nm. When the average particle diameter is more than 100 nm, the film becomes cloudy, the solution becomes unstable, and gelation becomes easy. When the average particle diameter is less than 2 nm, there is a case where the coating property is affected.

These may be used alone or in combination of two or more.

In the case where an organic cerium compound is used in combination, for example, a combination of vinyltrimethoxydecane and 3-methacryloxypropyltrimethoxydecane, vinyltrimethoxydecane and 3 may be preferably exemplified. a combination of glycidoxypropyltrimethoxydecane.

Further, as the organic ruthenium compound represented by the formula (I-1), the organic ruthenium compound having a carbon number of 3 or less of R ¹ is blended in an amount of 30 mol% or more, more preferably 50 to 100 mol%, more preferably R. the carbon number of ¹ or more of the organic silicon compound 4 blend 70 mole% or less, more preferably 0 to 50 mole%.

As another preferred aspect of the organic ruthenium compound used in the present invention, specifically, the solubility parameter SP1 of the above R determined by the Fedors algorithm is compared with the electromagnetic radiation obtained by the Fedors algorithm. The solubility parameter SP2 of the curable compound is 1.6 or more, preferably 1.6 to 8.5, more preferably 1.6 to 7.2, and the solubility parameter SP1 is less than 1.6 or less than the above solubility parameter SP1. The organic germanium compound Si2 having the same parameter SP2 or larger than the solubility parameter SP2 is composed of the organic germanium compound Si1 and the organic germanium compound Si2 having a molar ratio of Si1:Si2 of 5:5 to 10:0, more preferably 9: 1~10:0.

The organic cerium compound varies depending on the type of the electromagnetic radiation curable compound to be used. The solubility parameter (SP value) of the organic ruthenium compound and the electromagnetic radiation curable compound can be calculated based on the Fedors' push algorithm. Therefore, the combination of the organic ruthenium compound and the electromagnetic radiation curable compound can be determined based on the pre-calculated SP value.

In the above formula (I), when n is 2 and R is different, the SP value of the larger value is set to the above SP1, and the combination with the electromagnetic radiation curable compound is determined.

An example of an organic ruthenium compound which can be used in the present invention is shown in Table 1 below together with the SP value. Further, the compounds No. 1 to No. 15 correspond to the compound of the above formula (I-1).

"b) Hardened compound of electromagnetic radiation hardening compound"

The electromagnetic radiation curable compound to be used in the present invention is a compound or resin having a functional group which causes polymerization by irradiation of electromagnetic radiation in the presence of a polymerization initiator to be added as needed, as electromagnetic radiation to be used, Ultraviolet rays, X-rays, radiation, ionized radiation, ionizing radiation (α, β, γ ray, neutron ray, electron beam) can be used, preferably Contains light at wavelengths below 350 nm.

The irradiation of the electromagnetic radiation can be performed by using a known device such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp, a carbon arc lamp, or a xenon arc lamp, and the light source to be irradiated preferably comprises 150~. A light source of any wavelength in the range of 350 nm is more preferably a light source containing light of any wavelength in the range of 250 to 310 nm.

In addition, the amount of light to be irradiated by the composition for sufficiently curing the composition for forming an organic-inorganic composite film is, for example, about 0.1 to 100 J/cm ² , and the film hardening efficiency (the relationship between the irradiation energy and the degree of film hardening) is considered. It is preferably about 1 to 10 J/cm ² , more preferably about 1 to 5 J/cm ² .

Examples of the electromagnetic radiation curable compound include a (meth)acrylate compound, an epoxy compound, and a vinyl compound other than the acrylate compound. The number of the functional groups is not particularly limited as long as it is one or more. An example of the electromagnetic radiation curable compound used in the present invention can be listed together with the SP value in the second table below.

Further, in addition to the above compounds, as the acrylate-based compound, a polyurethane (meth) acrylate, a polyester (meth) acrylate, an epoxy poly(meth) acrylate, or the like may be used. Polyamine (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, and the like. The SP value of these compounds also depends on the type of functional group contained, and is in the range of 9-11.

The epoxy poly(meth) acrylate can be obtained, for example, by an esterification reaction of an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin with acrylic acid.

With regard to the polyester (meth) acrylate, for example, by using a polycarboxylic acid, The hydroxyl group of the polyester oligomer having a hydroxyl group at both terminals obtained by condensation of an acid with a polyol is esterified with acrylic acid. Alternatively, a hydroxyl group at the terminal of the oligomer obtained by addition of a polyvalent carboxylic acid and an alkylene oxide is obtained by esterification with acrylic acid.

The amine ester (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol with a diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyol include polyester polyol and polyether polyol. Alcohol, polycarbonate diol.

The commercial product of the amine ester (meth) acrylate used in the present invention is, for example, a product name: BEAMSET (registered trademark) 102, 502H, 505A-6, 510, 550B manufactured by Arakawa Chemical Industries Co., Ltd. , 551B, 575, 575CB, EM-90, EM92; trade name manufactured by San Nopco Co., Ltd.: Photomer (registered trademark) 6008, 6210; trade name manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U-324A, U-4H, U-6H; manufactured by Toagosei Co., Ltd.: ARONIX (registered trademark) M -1100, M-1200, M-1210, M-1310, M-1600, M-1960; trade names manufactured by Kyoeisha Chemical Co., Ltd.: AH-600, AT606, UA-306H; Nippon Chemical Co., Ltd. Trade name of the company: Kayarad (registered trademark) UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101; trade name manufactured by Japan Synthetic Chemical Industry Co., Ltd. : Violet (registered trademark) UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, UV-7600B, UV-2010B; Trade name of the company: Art resin (registered trademark) UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, H- 61. HDP-M20; goods manufactured by Daicel-UCB Co., Ltd. Name: Ebecryl (registered trademark) I6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301, and the like.

Among these, polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy poly(meth) acrylate, and more preferably polyurethane (meth) acrylate.

The molecular weight is indefinite as long as it can be dissolved in the composition for forming an organic-inorganic composite film, and the mass average molecular weight is preferably 500 to 50,000, more preferably 1,000 to 10,000.

The blending amount of the hardened material of the electromagnetic radiation curable compound in the organic-inorganic composite film, the solid content of the organic-inorganic composite film as a whole (the condensate of the organic cerium compound, the hardened compound of the electromagnetic radiation curable compound) The total mass of the other components to be blended as needed is preferably from 2 to 98% by mass, more preferably from 50 to 95% by mass, even more preferably from 70 to 95% by mass.

In the present invention, a polymerization initiator may be mixed, and as such an initiator, a compound which generates a cationic species by irradiation with electromagnetic radiation and a compound which generates an active radical species by irradiation with electromagnetic radiation may be mentioned. Starting agent.

<(A) Method for producing organic-inorganic composite film>

[Preparation of a solution for forming an organic-inorganic composite film]

In the solution for forming the organic-inorganic composite film of the present invention (A), in addition to the organic ruthenium compound and the electromagnetic radiation curable compound, a metal compound having a polymerization initiator, a decyl alcohol condensation catalyst, or the like, water and/or is appropriately mixed. Or prepared by solvent or the like.

Further, specific examples of the metal compound used as the decyl alcohol condensation catalyst include a metal alkoxide, a metal chelate compound, an organic acid metal salt or the like, and the like, and more specifically, It can be exemplified by tetraisopropoxy titanium, diisopropoxy Titanium diacetate pyruvate, or a hydrolysis condensate thereof, or the like.

The production method is not particularly limited, and specific examples thereof include a method in which a metal compound such as a metal chelate compound is mixed into a solvent, a specific amount of water is added, (partial) hydrolysis, and then an organic ruthenium compound (partial) is added. Hydrolysis is carried out. On the other hand, a heat or electromagnetic radiation curable compound is dissolved in a solvent, a polymerization initiator or a hardener is added as needed, and then the two solutions are mixed. These four components may be mixed at the same time, and a method of mixing the organic ruthenium compound and the metal compound may be exemplified by a method in which an organic ruthenium compound and a metal compound are mixed, and then (partially) hydrolyzed by adding water or organic ruthenium A method in which a compound and a metal compound are separately (partially) hydrolyzed. It is not necessary to add water or a solvent, but it is preferred to add water in advance to prepare a (partial) hydrolyzate. The amount of the specific amount of water depends on the kind of the metal compound. For example, when the metal compound is a metal compound having two or more hydroxyl groups or a hydrolyzable group, it is preferably used in the case of the metal compound 1 molar. For water above the ear, it is better to use 0.5~2 moles of water. Further, in the case where the metal compound is a metal chelate compound or an organic acid metal salt, it is preferably used in an amount of 5 to 100 mols of water, more preferably 5~, relative to the metal chelate compound or the organic acid metal salt 1 mol. 20 moles of water.

As the condensate of the a) organic hydrazine compound, the organic hydrazine compound (partially) may be hydrolyzed by a known decyl alcohol condensation catalyst.

The composition for forming an organic-inorganic composite film preferably contains water, a solvent, or the like in addition to the above components.

The solvent to be used is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and octane; and alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; tetrahydrofuran, Ethers such as alkyl ethers; esters such as ethyl acetate and butyl acetate; decylamines such as N,N-dimethylformamide and N,N-dimethylacetamide; Classes; alcohols such as methanol and ethanol; polyol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. These solvents may be used alone or in combination of two or more.

Examples of the stanol condensation catalyst include an acid, a base, and the like in addition to the above metal compound.

Examples of the acid include an organic acid and an inorganic acid. Specific examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, citric acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. Examples of the acid include hydrochloric acid, nitric acid, boric acid, and fluoroboric acid.

Here, specifically, the photoacid generator which generates an acid by light irradiation also includes diphenylphosphonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate or the like.

Examples of the base include strong bases such as tetramethylguanidine and tetramethylguanidinopropyltrimethoxydecane; organic amines, carboxylic acid neutralized salts of organic amines, and quaternary ammonium salts.

The solid content component in the solution for forming an organic-inorganic composite film of the present invention is preferably from 1 to 98% by mass, more preferably from 10 to 60% by mass, still more preferably from 15 to 45% by mass.

[(A) Manufacture of organic-inorganic composite film]

(A) The organic-inorganic composite film can be produced by applying a solution for forming the above-mentioned organic-inorganic composite film onto a resin substrate, drying and/or heating, and performing a plasma treatment or a UV ozone treatment.

Regarding the (A) organic-inorganic composite film, it is preferred that the concentration of carbon atoms at a depth of 10 nm from the surface as determined by ESCA analysis is thicker than the carbon atom at a depth of 100 nm from the surface. A film that is less than 20% less.

Here, the "carbon atom concentration" means the molar concentration of carbon atoms when (total metal atom + oxygen atom + carbon atom) is 100%. The concentrations of other elements are also the same.

As a coating method of the solution for forming an organic-inorganic composite film, a known coating method can be used, and examples thereof include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, and a curtain coating method. Gravure printing method, screen printing method, inkjet method, and the like. Further, the film thickness to be formed is not particularly limited, and is, for example, about 0.1 to 20 μm.

The drying and heat treatment of the film formed by applying the solution for forming an organic-inorganic composite film is preferably carried out at about 40 to 200 ° C for about 0.5 to 120 minutes, more preferably at 60 to 160 ° C for about 1 to 60 minutes, and further It is preferably about 60 to 120 ° C for about 1 to 60 minutes.

The insulating layer is constituted by the above-described configuration as a gate insulating film. Therefore, in the organic thin film transistor, the affinity between the insulating layer and the organic semiconductor layer is improved, and leakage current can be suppressed. Organic thin film transistors have practical carrier mobility.

[Organic Semiconductor Layer]

As a material constituting the organic semiconductor layer of the organic thin film transistor, a π-conjugated material can be used, and for example, polypyrrole, poly(N-substituted pyrrole), poly(3-substituted pyrrole), poly(3,4-di) can be used. Polypyrroles such as pyrrole); polythiophenes such as polythiophenes, poly(3-substituted thiophenes), poly(3,4-disubstituted thiophenes), polybenzothiophenes, polyisobenzothiophenes, and the like Polythiophene acetylenes such as polythiophene acetylene; poly(p-phenylacetylene) such as poly(p-phenylacetylene), polyaniline, poly(N-substituted aniline), poly(3-substituted aniline), poly(2) Polyaniline such as polyaniline or polyacetylene; polydiacetylene such as polydiacetylene, polyfluorene such as polyfluorene, polyfluorene such as polyfluorene, polycarbazole, poly(N-substituted) Polycarbazoles such as carbazoles and polyselenes; polyfurans such as polyfuran and polybenzofuran; poly(p-benzene)s such as poly(p-phenylene); polyfluorenes Class Concentration Classes; thick tetraphenyl, fused pentabenzene, hexabenzene, hexabenzene, dibenzo pentacene, tetraphenyl pentacene, anthracene, dibenzopyrene, , ruthenium, osmium, terrylene, egg benzene, quaterrylene, circummanthracene and other polyacenes; replacing one of the polyacene carbons with N, S, O a derivative of a functional group such as an atom or a carbonyl group (tribenzoic acid) Tribenzothiazide a polycyclic condensate as described in Japanese Laid-Open Patent Publication No. Hei 11-195790, which is a condensed hexabenzene, a hexafluorene, a polyphenylene sulfide, or a polyvinylene sulfide. Wait.

Further, it is also preferred to use α-hexathiophene α, ω-dihexyl-α-hexathiophene, α,ω-dihexyl-α- as the thiophene hexamer having the same repeating unit as the polymers. An oligomer such as quinquetliophene, α,ω-bis(3-butoxypropyl)-α-hexathiophene or styrylbenzene derivative.

Further, a copper indigo or a metal indigo such as a fluorine-substituted copper indigo described in Japanese Patent Laid-Open Publication No. Hei 11-251601; naphthalene 1,4,5,8-tetracarboxylic acid diimine, N , N'-bis(4-trifluoromethylbenzyl)naphthalene 1,4,5,8-tetracarboxylic acid diimine, and N,N'-bis(1H,1H-perfluorooctyl), N,N'-bis(1H,1H-perfluorobutyl) and N,N'-dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diimine derivatives, naphthalene 2,3,6 a condensed ring of a ruthenium tetracarboxylic acid such as a ruthenium tetracarboxylic acid such as a ruthenium dicarboxyimine such as a tetracarboxylic acid such as a tetracarboxylic acid and a ruthenium diamine of a ruthenium 2,3,6,7-tetracarboxylic acid. Dicarboxylic acid diamines; fullerenes such as C60, C70, C76, C78, C84; pigments such as SWNT and other carbon nanotubes, merocyanin pigments, hemicyanine pigments, etc. .

Among the π-conjugated materials, it is preferably selected from the group consisting of thiophene, vinylene, thiophene acetylene, phenylacetylene, para-phenylene, these or the like, or two or more of them as repeating units. And the number n of the repeating units is an oligomer of 4-10 or the number of the repeating units n It is at least one of a group consisting of a polymer of 20 or more, a condensed polycyclic aromatic compound such as fused pentabenzene, a fullerene, a condensed cyclic tetracarboxylic acid diimine, and a metal indigo.

Further, as another organic semiconductor material, tetrathiafulvalene (TTF)-tetracyanoquinone dimethane (TCNQ) complex, diexiethyltetrathiafulvalene (BEDTTTF)-perchloric acid can also be used. An organic molecular complex such as a complex, BEDTTTF-iodine complex, TCNQ-iodine complex. Further, a σ-conjugated polymer such as polydecane or polydecane or an organic-inorganic hybrid material described in JP-A-2000-260999 may be used.

Examples of the method for producing the organic semiconductor layer include a vacuum deposition method, a molecular beam epitaxy growth method, an ion beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, and a plasma polymerization method. , electrolytic polymerization, chemical polymerization, spray coating, spin coating, knife coating, dipping, casting, roll coating, bar coating, die coating, or LB Etc., can be used according to the material. However, in the above, in terms of productivity, a spin coating method, a knife coating method, a dip coating method, a roll coating method, a rod which can form a film simply and precisely using a solution of an organic semiconductor is preferable. Coating method, die coating method, casting method, and the like. Further, in terms of controlling the alignment of the molecular compound constituting the organic semiconductor layer, a gap casting method or an edge casting method which is a special casting method is preferred.

Further, as described in Advanced Material Magazine No. 6 of 1999, p480 to 483, for a precursor in which a precursor such as fused pentene is soluble in a solvent, heat treatment is performed on a film formed by coating a precursor. A film of the target organic material is formed.

The film thickness of the organic semiconductor layer is not particularly limited, and the characteristics of the obtained element are often affected by the film thickness of the active layer composed of the organic semiconductor, and the film thickness varies depending on the organic semiconductor, and is preferably 1 μm or less, particularly preferably 10 to 300 nm.

[dopant layer]

The organic thin film transistor of the present invention preferably has a dopant layer between the source electrode and the drain electrode and the organic semiconductor layer. As the dopant layer, for example, a material having a functional group such as acrylic acid, acetamide, dimethylamino group, cyano group, carboxyl group, or nitro group, or a benzofluorene derivative, tetracyanoethylene, and tetracyanide may be contained. a material that accepts electron acceptors, or a material having a functional group such as an amine group, a triphenyl group, an alkyl group, a hydroxyl group, an alkoxy group, or a phenyl group, such as a quinone dimethane or a derivative thereof Substituted amines such as phenylenediamine, anthracene, benzopyrene, substituted benzofluorenes, anthracene, substituted anthracene, carbazole and derivatives thereof, tetrathiafulvalene and derivatives thereof, etc. The body-like material is subjected to a so-called doping treatment.

The above doping treatment means that an electron-donating molecule (acceptor) or an electron-donating molecule (donor) is introduced as a dopant into the organic semiconductor layer. Therefore, the doped organic semiconductor layer is provided with a film containing the above condensed polycyclic aromatic compound and a dopant. As the dopant to be used in the present invention, a known one can be used.

Examples of the material used for the dopant layer include ferric chloride, TCNQ, F4TCNQ (tetrafluorotetracyanobenzoquinone dimethane), fullerene and derivatives thereof, and preferably F4TCNQ.

[Self-assembled monomolecular film]

Further, in order to increase the charge mobility of the organic semiconductor layer between the insulating layer and the organic semiconductor layer, a self-assembled monomolecular film (SAM) is preferably provided. Further, by providing the SAM, it is also possible to control the threshold voltage. Specific examples of the component for forming the SAM include octadecyltrichlorodecane, octadecyltrimethoxydecane, decyltrichlorodecane, decyltrimethoxydecane, and β-phenylethyltrichloride. Decane, β-phenethyltrimethoxydecane (β-PTS), trichloromethyl decazane, or alkane phosphoric acid, alkanephosphonic acid, alkane sulfonic acid, alkane carboxylic acid, and the like.

The organic thin film transistor of the present invention can be incorporated into various electronic devices for use. For example, it can be used as a driving element for active driving in various display devices such as a liquid crystal display device, an organic EL display device, and electronic paper, and can be used as a transistor element used in various sensors, and can be used in an electronic tag ( The IC tag) together with the capacitor constitutes a memory as an element.

[Examples]

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited by the examples.

[Production Example 1] (Preparation of solution for forming an organic-inorganic composite film)

Dissolved 30.3 g of diisopropoxy acetoacetate (manufactured by Nippon Soda Co., Ltd., T-50, solid content of titanium oxide: 16.5 wt%) to Solmix (registered trademark) AP-7 (Japan) After 58.4 g of Alcohol Trading Co., Ltd., 11.3 g of ion-exchanged water (10-fold molar relative to titanium) was slowly added dropwise while stirring to hydrolyze. After 1 day, the solution was filtered to obtain a titanium oxide nanoparticle dispersion [A-1] having a yellow transparent titanium oxide concentration of 5% by weight. The average particle diameter of titanium oxide is 4.1 nm and is monodisperse.

As the organic ruthenium compound, vinyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) (SP value: 7.00) and 3-methacryloxypropyltrimethoxy decane (Shin-Etsu Chemical) were used. Manufactured by Industrial Co., Ltd., KBM-503) (SP value: 9.48) mixed with a molar ratio of 7/3 (=vinyltrimethoxydecane/3-methylpropenyloxypropyltrimethoxydecane) Liquid [B-1].

The above [A-1] and [B-1] were mixed so as to have an element ratio (Ti/Si = 1/9), and a liquid [C-1] which was stirred for 12 hours was prepared. The solid content of [C-1] was 29.2% by weight.

As an electromagnetic radiation curable compound, an amine ester acrylate oligomer (synthetic in Japan) Manufactured by Societe Generale Co., Ltd., Violet UV1700B) (SP value: 10 to 11) dissolved in methyl isobutyl ketone (MIBK) in a form of 40% by weight. 1-hydroxy-cyclohexyl phenyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) as a photopolymerization initiator was dissolved in 4% by weight based on the solid content of the urethane acrylate oligomer. Solution, and make solution [D-1].

The above-mentioned [C-1] liquid and the [D-1] solution are mixed so that the ratio of the solid content becomes 10% by weight/90% by weight = [C-1] / [D-1], and an organic-inorganic composite is produced. Film forming solution [E-1].

[Example 1]

A polyethylene naphthalate film (PEN film) was used as the substrate. On the PEN film, a vacuum vapor deposition machine "EX-400" manufactured by ULVAC (vacuum degree: 1.3 × 10 ^-4 Pa) was used to sequentially deposit a chromium (Cr) layer having a thickness of 3 nm and a thickness. A 20 nm gold (Au) layer and a 5 nm thick chromium (Cr) layer form a gate electrode.

Then, the organic-inorganic composite film-forming solution [E-1] prepared in Production Example 1 was diluted to 4 times with a diluent, and the diluted liquid was applied to the gate in 20 seconds using a spin coater (2000 rpm). On the electrode, drying (hot air drying, 80 ° C, 3 minutes), ultraviolet irradiation (light collecting type high pressure mercury lamp, 160 W/cm, lamp height 9.8 cm, cumulative irradiation amount: about 500 mJ/cm ² ), and obtaining a film thickness of 650 nm Insulation layer.

Then, a PEN film having an insulating layer formed on the gate electrode was cut out to 2.5 × 2.5 cm ² .

Next, an organic semiconductor layer was formed in accordance with a coating method developed by the present inventors (edge casting: Apple. Phys. Exp. 2, 111501 (2009)). That is, a fragment of the crucible substrate for holding the solution (hereinafter also referred to as "solution holding structure") is placed on the PEN film which is cut out. An organic semiconductor solution (C10-DNBDT, manufactured by Pi-crystal Corporation) while tilting the substrate Drop the solution at 75 ° C to the edge of the solution retention structure. As the solvent evaporates, the crystal grows on one side and sticks to the substrate, and the crystal growth ends in a few minutes. In this state, the film was allowed to stand at room temperature for 1 hour under reduced pressure, and further allowed to stand at 100 ° C for 8 hours under reduced pressure to completely dry the crystal film (film thickness: 10 to 100 nm).

In order to fabricate the source-drain electrode on the organic semiconductor layer, a shadow mask of a channel (L: 100 μm, W: 2000 μm) was used to form a dopant layer of 1 nm thick composed of F4-TCNQ, and then 40 nm. The thickness is evaporated to gold, and a bottom gate-top contact type organic thin film transistor is fabricated.

The transmission characteristics were measured using a semiconductor parameter analyzer (model "keithley 4200", manufactured by Kaysley Instruments Co., Ltd.) for the produced organic thin film transistor.

1A shows the result of the saturated region of the organic thin film transistor of Example 1, and FIG. 1B shows the result of the linear region of the organic thin film transistor of Example 1.

From the results of FIG. 1A, the carrier mobility and the threshold voltage of the saturated region of the organic thin film transistor of Example 1 were calculated using the following formula (1).

Here, I _D is the drain current, W is the width of the channel, L is the length of the channel, μ is the carrier mobility, C _OX is the capacitance per unit area of the gate insulating film, and V _G is the gate voltage. V _T is the threshold voltage.

The drain voltage (V _D ) was set to -30 V, and the gate voltage (V _G ) was varied from 20 V to -30 V to measure the mobility. In the saturated region, a carrier mobility of 5.2 cm ² /Vs was obtained. The threshold voltage is 1.9V.

From the results of FIG. 1B, the carrier mobility and the threshold voltage of the linear region of the organic thin film transistor of Example 1 were calculated using the following formula (2).

The drain voltage (V _D ) was set to -1 V, and the gate voltage (V _G ) was varied from 20 V to -30 V, and the mobility was measured. In the linear region, a carrier mobility of 4.5 cm ² /Vs was obtained. The threshold voltage is -4.3V.

Further, the change in the carrier mobility with respect to the gate voltages obtained by the above formulas (1) and (2) is shown in FIGS. 2A and 2B. 2A is a carrier mobility (field-effect mobility) of a saturated region of the organic thin film transistor of Example 1, and FIG. 2B is a carrier mobility (effective mobility) of the organic thin film transistor of Example 1 in a linear region. . It is confirmed from Fig. 2A and Fig. 2B that the effective carrier mobility is shown with respect to the gate voltage.

Further, Fig. 3 shows the output characteristics of the organic thin film transistor of Example 1. The gate current (I _D ) and the gate voltage (V _G ), the gate current (I _D ) and the drain voltage (V _D ) all show a clear correlation, confirming that the organic transistor of Example 1 shows Excellent characteristics.

[Embodiment 2]

With respect to Example 2, β-phenethyltrichlorodecane (β-PTS) was formed on the insulating layer before the formation of the organic semiconductor layer on the PEN film on which the gate electrode and the insulating layer were formed (LP manufactured by Shin-Etsu Chemical Co., Ltd.) -1990) is different from Example 1 in terms of a self-assembled monomolecular film. For the self-assembled monomolecular film, a UV ozone cleaning device (manufactured by SEN LIGHTS Co., Ltd.) is used. The PEN film having the gate electrode and the insulating layer was subjected to UV ozone cleaning for 10 minutes, and further immersed in β-phenethyltrichloromethane for 18 hours to form an insulating layer.

In Example 2, the transfer characteristics were measured by the same method as in Example 1. 4A shows the result of the saturated region of the organic thin film transistor of Example 2, and FIG. 4B shows the result of the linear region of the organic thin film transistor of Example 2.

Based on the results of FIG. 4A, the carrier mobility and the threshold voltage of the saturated region were calculated. In the same manner as in the first embodiment, the gate voltage (V _D ) was set to -30 V, and the gate voltage (V _G ) was changed from 20 V to -30 V, and the mobility was measured. In the saturated region, a carrier mobility of 4.5 cm ² /Vs was obtained. The threshold voltage is 16V.

Further, based on the result of FIG. 4B, the carrier mobility and the threshold voltage of the linear region are calculated. In the same manner as in the first embodiment, the gate voltage (V _D ) was set to -1 V, and the gate voltage (V _G ) was changed from 20 V to -30 V, and the mobility was measured. In the linear region, a carrier mobility of 4.0 cm ² /Vs was obtained. The threshold voltage is 29V. It was confirmed that by forming the self-assembled monomolecular film, the threshold voltage can be controlled without largely changing the carrier mobility.

Further, in the same manner as in the first embodiment, the change in the carrier mobility with respect to the gate voltages obtained by the above formulas (1) and (2) is shown in FIGS. 5A and 5B. 5A is a carrier mobility (field-effect mobility) of a saturated region of the organic thin film transistor of Example 2, and FIG. 5B of the organic thin film transistor of Example 2 is a carrier mobility (effective mobility) in a linear region. ).

Further, Fig. 6 shows the output characteristics of the organic thin film transistor of Example 2. The gate current (I _D ) and the gate voltage (V _G ), the drain current (I _D ), and the drain voltage (V _D ) all indicate a clear correlation, confirming that the organic transistor of Example 2 shows excellent Characteristics.

[Industrial availability]

The organic thin film transistor of the present invention maintains adhesion to an organic semiconductor layer and exhibits practical carrier mobility.

Claims (6)

An organic thin film transistor comprising a gate insulating layer composed of an organic-inorganic composite film comprising the following a) and b), a) a condensate of an organic germanium compound represented by the formula (I), and b) an electromagnetic A cured product of a radiation curable compound, R _n SiX _4-n (I) (wherein R represents a carbon atom directly bonded to an organic group of Si, X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2, and n is At 2 o'clock, each R may be the same or different. When (4-n) is 2 or more, each X may be the same or different. The organic thin film transistor according to claim 1, wherein the organic germanium compound represented by the formula (I) is composed of an organic germanium compound Si1 and an organic germanium compound Si2, wherein the organic germanium compound Si1 is calculated by Fedors. The solubility parameter SP1 of the R obtained by the method is smaller than the solubility parameter SP2 of the electromagnetic radiation curable compound obtained by the Fedors algorithm, and the solubility parameter SP1 of the organic germanium compound Si2 is smaller than the solubility parameter SP2. 1.6 or equal to or greater than the solubility parameter SP2, the molar ratio of the organic germanium compound Si1 to the organic germanium compound Si2 is 5:5 to 10:0. The organic thin film transistor according to the first aspect of the invention, wherein the organic oxime compound represented by the formula (I) is a compound represented by the formula (I-1), a compound represented by the formula (I-2), and If present, it is composed of the hydrolysis condensate, R ¹ _n SiX _4-n . . . (I-1) (wherein, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ represents a vinyl group containing a vinyl group; It means that the hydroxyl group or the hydrolyzable group may be the same or different from each other) R ² _n SiX _4-n . . . (I-2) (wherein, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² represents an organic group other than a vinyl group-containing hydrocarbon group in which a carbon atom is directly bonded to Si in the formula. a group; a compound represented by the formula (I-1); Unit]}/{[Compound of the formula (I-1)]+[Compound of the formula (I-2)]+[If present, a unit derived from the compound of the formula (I-1) in the hydrolysis condensate ]+[If present, the unit derived from the compound of the formula (I-2) in the hydrolysis condensate]}×100=30-100 mol%, and {[the compound of the formula (I-2)]+[ If present, the unit derived from the compound of the formula (I-2) in the hydrolysis condensate]}/{[the compound of the formula (I-1)]+[the compound of the formula (I-2)]+[if present In the case of the hydrolysis condensate, the unit derived from the compound of the formula (I-1)] + [if present, the unit derived from the compound of the formula (I-2) in the hydrolysis condensate]} × 100 = 0~ 70% by mole. A display device comprising the organic thin film transistor according to any one of claims 1 to 3. A sensor comprising the organic thin film transistor according to any one of claims 1 to 3. An electronic label having the organic thin film transistor of any one of claims 1 to 3.