TWI506833B - Thin film transistor - Google Patents

Description

Thin film transistor

The present invention relates to a thin film transistor, and more particularly to a thin film transistor having a high mobility, a large on/off ratio, and a small leakage current.

In recent years, research related to organic TFTs (thin film transistors) using organic materials is prevailing. Such a thin film transistor is formed, for example, by forming a gate electrode, a gate insulating film, a semiconductor layer, a source electrode, and a drain electrode on the surface of the substrate.

In such a thin film transistor, a technique of using an organic semiconductor film is known as a semiconductor layer (refer to Patent Document 1). However, since the thin film transistor using such an organic semiconductor film has low carrier mobility and low responsiveness, when a thin film transistor using such an organic semiconductor film is applied to a display, flickering occurs on the screen. The problem of low definition. In response to this, a technique of using an amorphous oxide semiconductor such as indium gallium zinc oxide (IGZO) formed by a sputtering method as a semiconductor layer is reviewed.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Publication No. 2007-251093

However, when a semiconductor film made of an amorphous oxide semiconductor such as IGZO is formed by a sputtering method, the gate insulating film located under the semiconductor film is exposed to a high temperature condition or a plasma generating environment, and When the semiconductor film is formed by the influence of heat or plasma, the gate insulating film is deteriorated, and as a result, the on/off ratio becomes small and the leakage current increases.

An object of the present invention is to provide a thin film transistor having a high mobility, a large on/off ratio, and a small leakage current.

As a result of intensive studies to achieve the above object, the present inventors have found that a semiconductor film is made of a specific amorphous material in a thin film transistor including a gate insulating film and a semiconductor layer formed on the gate insulating film. A sputtering film made of an oxide semiconductor, and the gate insulating film is composed of a cyclic olefin polymer having a protic polar group and an epoxy group having two or more protonic polar groups in the molecule. The resin composition of the epoxy-based crosslinking agent is configured to achieve the above object, and the present invention has been completed.

That is, according to the present invention, there is provided a thin film transistor comprising a gate insulating film and a semiconductor layer formed on the gate insulating film, wherein the semiconductor layer contains at least one of In, Ga, and Zn. a sputtering film made of an amorphous oxide semiconductor of an element, wherein the gate insulating film contains a cyclic olefin polymer (A) having a protic polar group and two or more protons in a molecule. A resin composition of a cyclo-based epoxy-based crosslinking agent (B) which reacts with a polar group.

Preferably, in the foregoing resin composition, relative to the aforementioned cyclic olefin The content of the epoxy-based crosslinking agent (B) is 10 to 100 parts by weight based on 100 parts by weight of the polymer (A).

It is preferable that the resin composition contains two or more different compounds as the epoxy-based crosslinking agent (B).

It is preferred that the resin composition further contains a melamine-based crosslinking agent (C).

In the resin composition, the content of the melamine-based crosslinking agent (C) is preferably 10 to 50 parts by weight based on 100 parts by weight of the cyclic olefin polymer (A).

In the present invention, the thin film transistor may include a gate electrode provided on the substrate, a gate insulating film provided to cover the gate electrode, a semiconductor layer provided on a surface of the gate insulating film, and a semiconductor layer disposed on the gate electrode a source electrode and a drain electrode on the surface of the semiconductor layer, wherein the semiconductor layer is formed of a sputtering film made of an amorphous oxide semiconductor containing at least one of In, Ga, and Zn, and the gate insulating film A resin composition containing a cyclic olefin polymer (A) having a protic polar group and an epoxy crosslinking agent (B) having two or more epoxy groups reactive with a protic polar group in the molecule Composition.

Alternatively, in the present invention, the thin film transistor may include a gate electrode provided on the substrate, a gate insulating film provided to cover the gate electrode, and a portion covering the gate insulating film. a source electrode and a drain electrode, and a semiconductor layer provided across a surface of the gate insulating film, the source electrode, and the drain electrode, wherein the semiconductor layer is composed of at least one element including In, Ga, and Zn a sputtering film made of a crystalline oxide semiconductor, wherein the gate insulating film contains a cyclic olefin polymer (A) having a protic polar group and two or more protic polar groups in the molecule. The resin composition of the epoxy group-based epoxy crosslinking agent (B).

Further, in the present invention, the thin film transistor may include a gate electrode provided on the substrate, a gate insulating film provided to cover the gate electrode, a semiconductor layer provided on a surface of the gate insulating film, and An etch stopper provided on a portion of the surface of the semiconductor layer, and a source electrode and a drain electrode provided on a surface of the semiconductor layer and a portion of the surface on which the etching is stopped, the semiconductor layer including In, Ga And a sputtering film made of an amorphous oxide semiconductor of at least one element of Zn, wherein the gate insulating film contains a cyclic olefin polymer (A) having a protic polar group and has a molecular A resin composition of two or more epoxy-based crosslinking agents (B) which react with a protonic polar group.

According to the present invention, it is possible to provide a thin film transistor having a high mobility, a large on/off ratio, and a small leakage current.

1, 1a, 1b‧‧‧ film transistor

2‧‧‧Substrate

3‧‧‧gate electrode

4‧‧‧Gate insulation film

5‧‧‧Semiconductor layer

6‧‧‧Source electrode

7‧‧‧汲electrode

8‧‧‧etch stop

9‧‧‧Channel Department

Fig. 1 is a cross-sectional view showing an example of a thin film transistor of the present invention.

Fig. 2 is a cross-sectional view showing another example (second example) of the thin film transistor of the present invention.

Fig. 3 is a view showing a method of producing a thin film transistor of the present invention.

Fig. 4 is a cross-sectional view showing another example (third example) of the thin film transistor of the present invention.

The thin film transistor of the present invention has a gate insulating film and is formed on a thin film transistor of a semiconductor layer on the gate insulating film, wherein the semiconductor layer is formed of a sputtering film made of an amorphous oxide semiconductor containing at least one element selected from the group consisting of In, Ga, and Zn. The gate insulating film is composed of a cyclic olefin polymer (A) having a protic polar group and an epoxy crosslinking agent having two or more epoxy groups reactive with the protonic polar group in the molecule (B). The resin composition is composed of).

(resin composition)

The resin composition for forming a gate insulating film used in the present invention contains a cyclic olefin polymer (A) having a protic polar group and a ring having two or more protonic polar groups in the molecule. An epoxy-based crosslinking agent (B).

(Ring olefin polymer (A) having a protic polar group)

The cyclic olefin polymer (A) having a protic polar group used in the present invention (hereinafter simply referred to as "cyclic olefin polymer (A)") may, for example, be a cyclic olefin monomer of 1 or 2 or more. a polymer, or a copolymer of one or more cyclic olefin monomers, and a monomer copolymerizable therewith, but in the present invention, as a monomer for forming a cyclic olefin polymer (A) It is preferred to use a cyclic olefin monomer (a) having at least a protic polar group.

The protic polar group referred to herein means a group containing an atom to which a hydrogen atom is directly bonded to a group belonging to Group 15 or Group 16 of the periodic table. Among the atoms to which Group 15 or Group 16 of the periodic table belongs, an atom to which the first cycle or the second cycle of Group 15 or Group 16 of the periodic table belongs is more preferably an oxygen atom, a nitrogen atom or a sulfur atom. Particularly preferred is an oxygen atom.

Specific examples of such a protic polar group include, for example, a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group or a phosphoric acid group; a primary amino group, a secondary amino group, a primary guanamine group, a second guanamine group, a ruthenium group, etc. A polar group having a nitrogen atom; a polar group having a sulfur atom such as a thiol group or the like. Among them, those having an oxygen atom are preferred, and a carboxyl group is more preferred.

In the present invention, the number of protic polar groups to be bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and a heterogeneous polar group of a different type may be contained.

Specific examples of the cyclic olefin monomer (a) having a protic polar group (hereinafter referred to as a monomer (a) as appropriate) include, for example, 2-hydroxycarbonylbicyclo[2.2.1]hept-5- Alkene, 2-methyl-2-hydroxycarbonylbicyclo[2.2.1]-hept-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2,3- Dihydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 3-methyl-2-hydroxycarbonylbicyclo[2.2 .1]-hept-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo[2.2.1]-hept-5-ene, 2-hydroxycarbonyltricyclo[5.2.1.0 ^2,6 ]Te-3 , 8-diene, 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12- 9-ene, 4,5-dihydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]tau-9-ene, 4-carboxymethyl-4- Hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, N-(hydroxycarbonylmethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(hydroxycarbonylethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(hydroxycarbonylpentyl)bicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-(dihydroxycarbonyl Ethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(dihydroxycarbonylpropyl)bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-(hydroxycarbonylphenethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-(4-hydroxyphenyl)- 1-(Hydroxycarbonyl)ethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(hydroxycarbonylphenyl)bicyclo[2.2.1]hept-5-ene a carboxyl group-containing cyclic olefin such as 2,3-dicarboxy quinone imine; 2-(4-hydroxyphenyl)bicyclo[2.2.1]hept-5-ene, 2-methyl-2-(4- Hydroxyphenyl)bicyclo[2.2.1]hept-5-ene, 4-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 4-methyl 4-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 2-hydroxybicyclo[2.2.1]hept-5-ene, 2- Hydroxymethylbicyclo[2.2.1]hept-5-ene, 2-hydroxyethylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-hydroxymethylbicyclo[2.2.1]heptane- 5-ene, 2,3-dihydroxymethylbicyclo[2.2.1]hept-5-ene, 2-(hydroxyethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-methyl- 2-(Hydroxyethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)bicyclo[2.2. 1]hept-5-ene , 2-(2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropyl)bicyclo[2.2.1]hept-5-ene, 3-hydroxytricyclo[5.2.1.0 ^2,6 Deca-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.0 ^2,6 ]deca-4,8-diene, 4-hydroxytetracyclo[6.2.1.1 ^3,6 .0 ^{2, 7} ] Twelve-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 4,5-dihydroxymethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12- 9-ene, 4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]tau-9-ene, 4-methyl 4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, N-(hydroxyethyl)bicyclo[2.2.1]hept-5- A hydroxyl group-containing cyclic olefin such as a olefin-2,3-dicarboxy quinone imine or N-(hydroxyphenyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine. Among these, in view of increasing the adhesion of the obtained gate insulating film, a carboxyl group-containing cyclic olefin is preferable, and particularly preferably a 4-hydroxycarbonyltetracyclo group [6.2.1.1 ^3, 6.0] ^2,7 ] The 12-9-ene group, these monomers (a) may be used individually or in combination of 2 or more types.

In the cyclic olefin polymer (A), relative to the all monomer unit, The content of the unit of the monomer (a) is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, still more preferably from 30 to 70 mol%. When the content ratio of the unit of the monomer (a) is in the above range, the solubility of the cyclic olefin polymer (A) in a polar solvent is sufficient, and the strength and insulation properties when the gate insulating film is used can be improved.

Further, the cyclic olefin polymer (A) used in the present invention may also be a copolymer obtained by copolymerizing a cyclic olefin monomer (a) having a protic polar group and a monomer (b) copolymerizable therewith. Things. Examples of such a copolymerizable monomer include a cyclic olefin monomer (b1) having a polar group other than a protic polar group, a cyclic olefin monomer (b2) having no polar group, and a cyclic olefin. Monomer (b3) (hereinafter referred to as "monomer (b1)", "monomer (b2)", "monomer (b3)").

The cyclic olefin monomer (b1) having a polar group other than the protic polar group may, for example, be a cyclic olefin having an N-substituted quinone imine group, an ester group, a cyano group, an acid anhydride group or a halogen atom. .

The cyclic olefin having an N-substituted quinone imine group may, for example, be a monomer represented by the following formula (1) or a monomer represented by the following formula (2).

(In the above formula (1), R ¹ represents a hydrogen atom or an alkyl group or an aryl group having 1 to 16 carbon atoms, and n is an integer of 1 or 2.)

(In the above formula (2), R ² represents a divalent alkylene group having 1 to ³ carbon atoms, and R ³ represents a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkane having 1 to 10 carbon atoms. base.)

In the above formula (1), R ¹ is an alkyl group or an aryl group having 1 to 16 carbon atoms, and specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, and n-pentyl group. N-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexyl Alkenyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cyclodecyl, cyclododecyl, norbornyl, anthracene a cyclic alkyl group such as a thiol group, an isodecyl group, a decahydronaphthyl group, a tricyclodecanyl group or an adamantyl group; a 2-propyl group, a 2-butyl group, a 2-methyl-1-propyl group, a 2-methyl group -2-propyl, 1-methylbutyl, 2-methylbutyl, 1-methylpentyl, 1-ethylbutyl, 2-methylhexyl, 2-ethylhexyl, 4-methyl A branched alkyl group such as heptyl, 1-methylindenyl, 1-methyltridecyl or 1-methyltetradecyl. Further, specific examples of the aryl group include a benzyl group and the like. Among these, in view of further improving heat resistance and solubility in a polar solvent, an alkyl group or an aryl group having 6 to 14 carbon atoms is preferred, and an alkyl group or aryl group having a carbon number of 6 to 10 is more preferred. . When the carbon number is 4 or less, there is a concern that solubility in a polar solvent is poor, and when the carbon number is 17 or more, heat resistance is poor.

Specific examples of the monomer represented by the above formula (1) include bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-phenyl-bicyclo [ 2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-ethyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N- Butyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-adamantylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(1-methylbutyl)-bicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine, N-(2-methylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methyl Pentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2-methylpentyl)-bicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, N-(1-ethylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-ethyl butyl ))-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine, N-(2-A Hexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-methylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine, N-(1-butylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-butylpentyl) -bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-(2-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-methylheptyl)- Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(1-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(2-ethylhexyl)-bicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine , N-(1-propylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-propylpentyl)-bicyclo[2.2.1 Gh-5-ene-2,3-dicarboxy quinone imine, N-(1-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3 -methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-methyloctyl)-bicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(1-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2- Ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(3-ethylheptyl)-bicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(4-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-propane Cyclohexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-propylhexyl)-bicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine, N-(3-propylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methylindenyl) -bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2-methylindolyl)-bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-(3-methylindolyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-methylindenyl)- Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(5-methylindolyl)-bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(1-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine N-(2-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-ethyloctyl)-bicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(4-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -(1-methylindolyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(1-methylundecyl)-bicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(1-methyldodecyto)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methyltridecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(1-methyltetradecyl)-bicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methylpentadecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-phenyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene-4,5-dicarboxy quinone imine, N-(2,4-dimethoxy Phenyl)-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene-4,5-dicarboxy quinone imine, and the like. Further, these may be used alone or in combination of two or more.

On the other hand, in the above formula (2), R ² is a divalent alkylene group having 1 to 3 carbon atoms, and examples of the divalent alkylene group having 1 to 3 carbon atoms include a methylene group and a stretching group. Ethyl, propyl, isopropyl and the like. Among these, a methylene group and an ethyl group are preferred because of good polymerization activity.

Further, in the above formula (2), R ³ is a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkyl group having 1 to 10 carbon atoms. Examples of the monovalent alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, a hexyl group, and a cyclohexyl group. Examples of the monovalent halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a trifluoromethyl group, and a trichloromethyl group. , 2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, and perfluoropentyl. Among these, R ^{3 is} preferably a methyl group and an ethyl group because of its excellent solubility in a polar solvent.

Further, the monomer represented by the above formulas (1) and (2) can be obtained, for example, by a guanidation reaction of a corresponding amine with 5-northene-2,3-dicarboxylic anhydride. Further, the obtained monomer can be efficiently separated by separating and purifying the reaction liquid of the guanidination reaction by a known method.

Examples of the cyclic olefin having an ester group include 2-ethyloxybicyclo[2.2.1]hept-5-ene and 2-ethoxycarbonylmethylbicyclo[2.2.1]hept-5. - alkene, 2-methoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-propoxycarbonylbicyclo[2.2.1 Hept-5-ene, 2-butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-cyclohexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2 -Methoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-propoxy Carbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo[ 2.2.1]hept-5-ene, 2-(2,2,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-methyl-2-(2,2, 2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 4-ethenyloxytetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]t-12-ene, 4 -methoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 4-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12 -9-ene, 4-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 4-butoxycarbonyltetracyclo[6.2.1.1 ^{3 ,6} .0 ^2,7 ]12- 9-ene, 4-methyl-4-methoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12-9-ene, 4- Methyl-4-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 4-methyl-4-propoxycarbonyltetracyclo[6.2.1.1 ^{3, 6} .0 ^2,7 ] 12-9-ene, 4-methyl-4-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]tau-9-ene, 4-( 2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]t-12-ene, 4-methyl-4-(2,2,2-tri Fluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12-9-ene and the like.

Examples of the cyclic olefin having a cyano group include 4-cyanotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-9-ene, 4-methyl-4-cyano group. Tetracycline [6.2.1.1 ^3,6 .0 ^2,7 ] 12-9-ene, 4,5-dicyanotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12-9-ene 2-cyanobicyclo[2.2.1]hept-5-ene, 2-methyl-2-cyanobicyclo[2.2.1]hept-5-ene, 2,3-dicyanobicyclo[2.2.1 ]Hept-5-ene and the like.

Examples of the cyclic olefin having an acid anhydride group include a tetracyclic ring [6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene-4,5-dicarboxylic anhydride, bicyclo [2.2.1]. Hept-5-ene-2,3-dicarboxylic anhydride, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene anhydride, and the like.

Examples of the cyclic olefin having a halogen atom include 2-chlorobicyclo[2.2.1]hept-5-ene, 2-chloromethylbicyclo[2.2.1]hept-5-ene, 2-( Chlorophenyl)bicyclo[2.2.1]hept-5-ene, 4-chlorotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]tau-9-ene, 4-methyl-4-chlorotetra Ring [6.2.1.1 ^3,6 .0 ^2,7 ] 12-9-ene and the like.

These monomers (b1) may be used alone or in combination of two or more.

Specific examples of the cyclic olefin monomer (b2) having no polar group include, for example, bicyclo [2.2.1] hept-2-ene (also known as norbornene), 5-ethyl-bicyclo [ 2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methylene -bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[5.2.1.0 ^2,6 ]indole-3,8-diene (usually used) Name: dicyclopentadiene), tetracyclo[10.2.1.0 ^2,11 .0 ^4,9 ] fifteen-4,6,8,13-tetraene, tetracyclo[6.2.1.1 ^3,6 .0 ^{2 , 7} ] dodec-4-ene (also known as tetracyclododecene), 9-methyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-B Tetracyclic [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-4-ene, 9-methylene-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene , 9-ethylene-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-vinyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12 4-ene, 9-propenyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 .0 ^{4, 8} ] fifteen-5,12-diene, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, anthracene, 3a, 5, 6, 7a-tetrahydro-4,7-bridge methylene (methano) )-1H-indole, 9-phenyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, tetracyclo[9.2.1.0 ^2,10 .0 ^3,8 ] -3,5,7,12-tetraene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 .0 ^4,8 ] fifteen-12-ene and the like.

These monomers (b2) may be used alone or in combination of two or more.

Specific examples of the monomer (b3) other than the cyclic olefin are, for example, For example: ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentyl Alkene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4- Ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-18 Alkenes, 1-eicosene and other α-olefins having 2 to 20 carbons; 1,5-hexadiene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-A Non-conjugated dienes such as 1,4-hexadiene and 1,7-octadiene, and derivatives thereof. Among these, an α-olefin is preferred, and ethylene is particularly preferred.

These monomers (b3) may be used alone or in combination of two or more.

Among the monomers (b1) to (b3), the effect of the present invention is From the viewpoint of a single step, a cyclic olefin monomer (b1) having a polar group other than a protic polar group is preferred, and a cyclic olefin having an N-substituted quinone imine group is particularly preferred.

In the cyclic olefin polymer (A), relative to the all monomer unit, The content of the unit of the copolymerizable monomer (b) is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, still more preferably from 30 to 70 mol%. When the content ratio of the unit of the copolymerizable monomer (b) is in the above range, the solubility of the cyclic olefin polymer (A) in a polar solvent is sufficient, and the strength and insulation as a gate insulating film can be made. Good sex.

Moreover, in the present invention, a known modifier can also be used. A protic polar group is introduced into the cyclic olefin polymer having no protic polar group to obtain a cyclic olefin polymer (A).

The polymer having no protic polar group can be obtained by arbitrarily combining and polymerizing at least one of the monomer (b1) and the monomer (b2) with the monomer (b3) which is required.

A modifier used to introduce a protic polar group, usually one point A compound having a protic polar group and a reactive carbon-carbon unsaturated bond in the sub.

Specific examples of such a compound include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, and erucic acid. Acid), brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid, cinnamic acid and other unsaturated carboxylic acids; allyl alcohol , methyl vinyl methanol, crotyl alcohol, 2-methylallyl alcohol, 1-phenylvinyl-1-ol, 2-propen-1-ol, 3-buten-1-ol, 3 -buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, An unsaturated alcohol such as 2-methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol or 2-hexen-1-ol; Wait.

The modification reaction of the cyclic olefin polymer using such modifiers can be carried out according to a usual method, usually in the presence of a radical generating agent.

Moreover, the cyclic olefin polymer (A) used in the present invention may The ring-opening polymer obtained by ring-opening polymerization of the above monomer or the addition polymer obtained by addition polymerization of the above monomer is preferably an open ring from the viewpoint of further enhancing the effect of the present invention. polymer.

Ring-opening polymer, which can utilize a ring having a protic polar group The olefin monomer (a) and, if necessary, the copolymerizable monomer (b) are produced by ring-opening shift polymerization in the presence of a shift-shifting reaction catalyst. As the production method, for example, the method described in [0039] to [0079] of International Publication No. 2010/110323 can be used.

The weight average of the cyclic polyolefin polymer (A) used in the present invention The molecular weight (Mw) is usually from 1,000 to 1,000,000, preferably from 1,500 to 100,000, more preferably from 2,000 to 10,000.

Further, the molecular weight distribution of the cyclic polyolefin polymer (A) is usually 4 or less, preferably 3 or less, more preferably 2.5 or less, in terms of a weight average molecular weight/number average molecular weight (Mw/Mn) ratio. Further, the weight average molecular weight (Mw) or molecular weight distribution (Mw/Mn) of the cyclic polyolefin polymer (A) can be measured by a gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as a solution. The value obtained as a polystyrene-converted value.

(Epoxy crosslinking agent having two or more epoxy groups in the molecule) (B))

The resin composition for forming a gate insulating film used in the present invention contains two or more and a cyclic polyolefin polymer (A) in addition to the above-mentioned cyclic polyolefin polymer (A). The epoxy-based epoxy crosslinking agent (B) which reacts with a protonic polar group (hereinafter simply referred to as "epoxy crosslinking agent (B)").

In the present invention, as a resin group for forming a gate insulating film By using the cyclic polyolefin polymer (A) and the epoxy crosslinking agent (B), the heat resistance and the plasma resistance of the obtained gate insulating film can be improved, and thus even When sputtering for forming a semiconductor film is performed, deterioration of the gate insulating film caused by heat or plasma generated during sputtering is effective Prevention. Then, the thin film transistor obtained in this manner can be a thin film transistor having a high mobility, a large on/off ratio, and a small leakage current.

The epoxy-based crosslinking agent (B) used in the present invention is as long as it is The compound having two or more epoxy groups reactive with the protic polar group of the cyclic polyolefin polymer (A) in the molecule is not particularly limited. Further, as the epoxy group, any of a terminal epoxy group and an alicyclic epoxy group may be used.

As such an epoxy-based crosslinking agent (B), for example, a bisphenol A type Epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, polyphenol epoxy resin, cyclic aliphatic epoxy resin, epoxy propyl ether compound , epoxy acrylate polymer, and the like.

Specific examples of the epoxy-based crosslinking agent (B) are, for example, two rings. Trifunctional epoxy compound having a pentadiene skeleton (trade name "XD-1000", manufactured by Nippon Kayaku Co., Ltd.), 1,2-epoxy of 2,2-bis(hydroxymethyl)1-butanol 4-(2-oxiranyl)cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, trade name "EHPE 3150", Daicel Chemical Industry Co., Ltd., epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis(3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, commercial product) "EPOLEAD GT 301", manufactured by Daicel Chemical Industry Co., Ltd.), epoxidized butane tetracarboxylate (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic 4-functional epoxy resin) An epoxy compound having an alicyclic structure such as "EPOLEAD GT 401", manufactured by Daicel Chemical Industry Co., Ltd.); an aromatic amine type polyfunctional epoxy compound (trade name "H-434", manufactured by Tohto Kasei Co., Ltd.), Cresol novolac type polyfunctional epoxy compound (trade name "EOCN-1020", manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type multifunctional epoxy Compound ("Epicoat 152, Epicoat 154", manufactured by Japan Epoxy Resin Co., Ltd.), a polyfunctional epoxy compound having a naphthalene skeleton (trade name "EXA-4700", manufactured by Dainippon Printing Chemical Co., Ltd.), and a chain alkyl group Polyfunctional epoxy compound (trade name "SR-TMP", manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyfunctional epoxy polybutadiene (trade name "EPOLEAD PB3600", manufactured by Daicel Chemical Industry Co., Ltd.), and epoxy propyl group of glycerin Polyether compound (trade name "SR-GLG", manufactured by Sakamoto Pharmaceutical Co., Ltd.), diglycerin polyglycidyl ether compound (trade name "SR-DGE", manufactured by Sakamoto Pharmaceutical Co., Ltd.), poly An epoxy compound having no alicyclic structure, such as a glycerol polyglycidyl ether compound (trade name "SR-4GL", manufactured by Sakamoto Pharmaceutical Co., Ltd.).

In the epoxy-based crosslinking agent (B), the obtained gate insulating film From the viewpoint of high heat-improving effect, a compound having an alicyclic structure is preferable, and a compound having an alicyclic structure and having an epoxy group of three or more is more preferable.

Moreover, the heat resistance and plasma resistance of the resulting gate insulating film In view of the sputtering for forming a semiconductor film, the effect of suppressing the deterioration of the gate insulating film caused by heat or plasma generated during sputtering can be further improved. Further, as the epoxy-based crosslinking agent (B), it is preferred to use two or more different compounds in combination. In this case, the two or more different compounds may be two or more compounds which can be determined to be substantially different in chemical structure. For example, the above compounds may be used in combination as appropriate. From the viewpoint that the effect of improving the heat resistance is higher, a compound having a molecular weight (Mw) of less than 1,000 (preferably 800 or less) is preferably used in combination with a compound having a molecular weight (Mw) of 1,000 or more (preferably 2,000 or more). Or, the same effect can improve the heat resistance and the plasma resistance. It is also preferred to use a compound having a terminal epoxy group in combination with an alicyclic epoxy group.

Epoxy crosslinking agent in the resin composition used in the present invention The content of (B) is preferably 10 to 100 parts by weight, more preferably 20 to 70 parts by weight, still more preferably 40 to 60 parts by weight, per 100 parts by weight of the cyclic polyolefin polymer (A). When the content of the epoxy-based crosslinking agent (B) is in the above range, the heat resistance and the plasma resistance of the obtained gate insulating film can be appropriately improved.

(melamine crosslinker (C))

The resin composition for forming a gate insulating film used in the present invention preferably contains a melamine-based compound in addition to the above-mentioned cyclic polyolefin polymer (A) and epoxy-based crosslinking agent (B). Joint agent (C). By further containing the melamine-based crosslinking agent (C), the heat resistance and the plasma resistance of the obtained gate insulating film can be further improved, and thus, when sputtering is performed for forming a semiconductor film, sputtering is performed. The effect of suppressing the deterioration of the gate insulating film caused by the generated heat or plasma can be further improved.

As the melamine crosslinking agent (C) used in the present invention, only If it has a melamine skeleton and reacts with the cyclic polyolefin polymer (A) to form a crosslinked structure between the cyclic polyolefin polymers (A), in the present invention, it is preferred to use The compound represented by the formula (3).

In the above formula (3), R ⁴ to R ^{9 each} independently represent a hydrogen atom or a -CH ₂ OR ¹⁰ group (wherein R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and at least R ⁴ to R ⁹ are at least One is -CH ₂ OR ¹⁰ base. R ⁴ to R ⁹ may be the same or different from each other. Further, in the above formula (3), among the alkoxymethyl groups having 1 to 6 carbon atoms represented by the -CH ₂ OR ¹⁰ group, it is preferred that the carbon number of R ¹⁰ is an alkoxy group having 1 to 4 carbon atoms. The methyl group is specifically a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group or a butoxymethyl group, and particularly preferably a methoxymethyl group.

Specific examples of the melamine-based crosslinking agent (C) are, for example, Examples of the melamines which may have a methylol group or an imine group such as N, N, N', N', N", N"-(hexaalkyloxyalkyl) melamine (trade names "CYMEL303, CYMEL325, CYMEL350, CYMEL370, CYMEL232, CYMEL235, CYMEL272, CYMEL212, mycoat 506" (above, Cytech Industries, etc.) Cymel series, Mycoat series).

About 100 parts by weight of the cyclic polyolefin polymer (A), the hair The content of the melamine-based crosslinking agent (C) in the resin composition used is preferably from 10 to 100 parts by weight, more preferably from 10 to 50 parts by weight, still more preferably from 20 to 50 parts by weight. Further, the relationship between the content of the melamine-based crosslinking agent (C) and the epoxy-based crosslinking agent (B) is the weight ratio of the "epoxy crosslinking agent (B): melamine crosslinking agent (C)". Preferably, it is in the range of 1:3 to 3:1, more preferably in the range of 1:2 to 2:1. When the content of the melamine-based crosslinking agent (C) is in the above range, the heat resistance and the plasma resistance of the obtained gate insulating film can be appropriately improved.

(other compounding agents)

The resin composition used in the present invention may further contain a solvent. As The solvent is not particularly limited, and examples of known solvents for the solvent of the resin composition include acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, and 3-heptanone. And linear ketones such as 4-heptanone, 2-octanone, 3-octanone and 4-octanone; alcohols such as n-propanol, isopropanol, n-butanol and cyclohexanol; Ethers such as ether, ethylene glycol diethyl ether and dioxane; alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, and propionic acid Methyl ester, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate and other esters; 赛路苏 acetate, methyl sarbuta acetate, ethyl 赛路苏Berthoyl esters such as acetate, propyl ceramide acetate, butyl sarbuta acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol such as propylene glycol monobutyl ether; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether Γ-butyrolactone, Saturated γ-lactones such as γ-valerolactone, γ-caprolactone, and γ-octanolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; dimethylacetamide; A polar solvent such as dimethylformamide or N-methylacetamide. These solvents may be used singly or in combination of two or more. The content of the solvent is preferably from 10 to 10,000 parts by weight, more preferably from 50 to 5,000 parts by weight, still more preferably from 100 to 1,000 parts by weight, based on 100 parts by weight of the cyclic polyolefin polymer (A). Further, when a solvent is contained in the resin composition, the solvent is usually removed after the gate insulating film is formed.

Moreover, the resin composition used in the present invention does not interfere with the present invention. The range of the effect can be expected to contain an antioxidant, a surfactant, a compound having an acidic group or a thermolatent acidic group, a coupling agent or a derivative thereof, a sensitizer, a photostabilizer, an antifoaming agent, a pigment, a dye, Other compounding agents such as fillers. this Among them, for example, a coupling agent or a derivative thereof, a sensitizer, and a photostabilizer can be used as described in Japanese Laid-Open Patent Publication No. 2011-75609.

As the antioxidant, there is no particular limitation, and the usual one can be used. A phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, or the like used for the polymer. By containing an antioxidant, the light resistance and heat resistance of the obtained gate insulating film can be improved.

As a phenolic antioxidant, for example, it can be used: 2-third -6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-p-pentyl-6-[1-(3 An acryl-based compound described in JP-A-63-179953, or JP-A-1-166643, which is the same as the above-mentioned Japanese Patent Laid-Open Publication No. Hei. No. Hei. 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylene-bis-(6-third P-cresol), 4,4'-thiobis-(3-methyl-6-tert-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanyloxy]-1,1-dimethylethyl]-2, 4,8,10-oxospiro[5,5]undecane, 1,1,3-gin(2-methyl-4-hydroxy-5-t-butylphenyl)butane, pentaerythritol-ruthenium [3-(3,5-Di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylbenzene) Alkyl-substituted phenolic compound such as propionate], tocopherol; 6-(4-hydroxy-3, 5-di-t-butylanilino)-2,4-bis-octylsulfide-1,3,5-triazine (triazine), 6-(4-hydroxy-3,5-dimethylanilino) -2,4-bis-octylsulfide-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis-octyl Sulfur-1,3,5-triazine, 2-octylsulfide-4,6-bis-(3,5- A triazinylphenol-containing compound such as di-tert-butyl-4-oxoanilino-1,3,5-triazine or the like.

As a phosphorus-based antioxidant, as long as it is a general resin industry, it is usually The user can be used without particular limitation, and for example, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, decyl (nonylphenyl) can be used. Phosphite, ginseng (dinonylphenyl) phosphite, ginseng (2,4-di-t-butylphenyl) phosphite, ginseng (2-tert-butyl-4-methylphenyl) Phosphite, cis (cyclohexylphenyl) phosphite, 2,2'-methylenebis(4,6-di-t-butyl)octyl phosphite, 9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphanthene- a monophosphite compound such as 10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphinophene; 4,4'-butylene-bis(3-methyl -6-t-butyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis[phenyldialkyl(C12-C15) phosphite], 4,4'- Isopropyl-bis[diphenylmonoalkyl (C12~C15) phosphite], 1,1,3-glycol (2-methyl-4-di-tridecylphosphite-5- Tributylphenyl)butane, anthracene (2,4-di-t-butylphenyl)-4,4'-biphenyldiphosphite, cyclopentanetetraylbis(octadecylphosphoric acid ), cyclopentane tetrakis(bis(isodecylphosphite), cyclopentanetetraylbis(nonylphenylphosphite), cyclopentanetetraylbis (2,4'-di Tributylphenylphosphite), cyclopentane tetrakis(2,4-dimethylphenylphosphite), cyclopentanetetraylbis(2,6-di-t-butylbenzene) A bisphosphite compound such as a phosphite. Among them, a monophosphite compound is preferred, and a quinone (nonylphenyl) phosphite, a ginsyl (diphenyl) phosphite, and a ginseng (2, 4- and a third) are preferred. Butyl phenyl) phosphite and the like.

As a sulfur-based antioxidant, for example, it can be used: 3,3'-thiodipropyl Dilauryl acid ester, 3,3'-thiodipropionate dimyristyl ester, 3,3'-dithiolactyl distearyl ester, 3,3'-thiodipropionate lauryl stearyl ester, pentaerythritol bismuth - (β-lauryl thiopropionate), 3,9-bis(2-dodecylthioethyl)-2,4,8,10-oxaoxaspiro[5,5]undecane, and the like.

Among these, phenol-based antioxidants are preferred, and more preferably quarters. Pentaerythritol oxime [3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate].

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

About 100 parts by weight of the cyclic polyolefin polymer (A), the hair The content of the antioxidant in the resin composition used is preferably from 0.1 to 10 parts by weight, more preferably from 1 to 5 parts by weight. When the content of the antioxidant is within the above range, a gate insulating film having excellent light resistance and heat resistance of the gate insulating film can be obtained.

Surfactant is for the prevention of streaks (coating streaks), etc. Used for purposes. Examples of the surfactant include an anthrone-based surfactant, a fluorine-based surfactant, a polyoxyalkylene-based surfactant, a methacrylic copolymer-based surfactant, and an acrylic copolymer-based surfactant.

Examples of the anthrone-based surfactant include, for example: "SH28PA", "SH29PA", "SH30PA", "ST80PA", "ST83PA", "ST86PA", "SF8416", "SH203", "SH230", "SF8419", "SF8422", "FS1265", "SH510" "SH550", "SH710", "SH8400", "SF8410", "SH8700", "SF8427" (above is Toray Dow Corning), trade names "KP-321", "KP-323", " KP-324", "KP-340", "KP-341" (above is Shin-Etsu Chemical Industry Co., Ltd. System), trade names "TSF400", "TSF401", "TSF410", "TSF4440", "TSF4445", "TSF4450", "TSF4446", "TSF4452", "TSF4460" (above is Momentive Performance Materials Japan contract company ), the product names "BYK300", "BYK301", "BYK302", "BYK306", "BYK307", "BYK310", "BYK315", "BYK320", "BYK322", "BYK323", "BYK331", "BYK333" ", "BYK370", "BYK375", "BYK377", "BYK378" (above, BYK Japan).

Examples of the fluorine-based surfactant include: Fluorient "FC-430", "FC-431" (above, Sumitomo 3M Co., Ltd.), Surflon "S-141", "S-145", and " S-381", "S-393" (above is manufactured by Asahi Glass Co., Ltd.), Eftop (registered trademark) "EF301", "EF303", "EF351", "EF352" (above, JEMCO Co., Ltd.), MEGAFACE (registered trademark) "F171", "F172", "F173", "R-30" (above is DIC Corporation).

Examples of the polyoxyalkylene-based surfactant include polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethyl ether ether, and polyoxyethyl octyl benzene. Polyoxyalkylene ethers such as ethers, polyoxyethylidene phenyl ethers, polyoxyethylene ethyl dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate Classes, etc.

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

The content of the surfactant in the resin composition used in the present invention is preferably 0.01 to 0.5 part by weight, more preferably 0.02 to 0.2 part by weight, based on 100 parts by weight of the cyclic polyolefin polymer (A). When the content of the surfactant is within the above range, the effect of preventing streaks (coating streaks) can be improved.

a compound having an acidic group or a thermolatent acidic group, as long as it has The acidic group may be a thermotropic acidic group which generates an acidic group by heating, and is not particularly limited, and is preferably an aliphatic compound, an aromatic compound or a heterocyclic compound, more preferably an aromatic compound or a heterocyclic compound.

These compounds having an acidic group or a thermolatent acidic group may be used singly or in combination of two or more.

An acidic group of a compound having an acidic group or a thermolatent acidic group The number of the acidic latent acidic groups is not particularly limited, and it is preferred to have a total of two or more acidic groups and/or a thermolabile acidic group. The acidic groups or the thermally latent acidic groups may be the same or different from each other.

The acidic group may be an acidic functional group, and specific examples thereof include a strongly acidic group such as a sulfonic acid group or a phosphoric acid group; and a weakly acidic group such as a carboxyl group, a thiol group or a carboxymethylenethio group. Among these, a carboxyl group, a thiol group or a carboxymethylenethio group is preferred, and a carboxyl group is particularly preferred. Further, among these acidic groups, the acid dissociation constant pKa is preferably in the range of 3.5 or more and 5.0 or less. Further, when two or more acidic groups are present, the first dissociation constant pKa1 is an acid dissociation constant, and the first dissociation constant pKa1 is preferably in the above range. Further, the pKa was measured under a dilute aqueous solution condition, and the acid dissociation constant Ka = [H ₃ O ⁺ ] [B ^- ] / [BH] was measured, and pKa = -logKa. Here, BH represents an organic acid, and B- represents a conjugate base of an organic acid.

Further, the measurement method of pKa is, for example, a hydrogen ion concentration measured using a pH meter, and is calculated from the concentration of the substance and the hydrogen ion concentration.

Moreover, the hot latent acidic group is only acidic by heating. The functional group may be a group, and specific examples thereof include a phosphonium salt group, a benzothiazole salt group, an ammonium salt group, a phosphonium salt group, and a blocked carboxylic acid group. this Among them, a blocked carboxylic acid group is preferred. Further, the terminal blocking agent for obtaining a carboxyl group used for blocking the carboxylic acid group is not particularly limited, and is preferably a vinyl ether compound.

Further, the compound having an acidic group or a thermolatent acidic group may have a substituent other than an acidic group and a thermolatent acidic group.

Such a substituent is, for example, a hydrocarbon group such as an alkyl group or an aryl group; in addition to, for example, a halogen atom; an alkoxy group, an aryloxy group, a decyloxy group, a heterocyclic oxy group; an alkyl group, an aryl group or a heterocyclic group; Substituted amine group, mercaptoamine group, ureido group, amine sulfonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group; alkylthio group, arylthio group, heterocyclic thio group; A polar group of a proton, a hydrocarbon group substituted with such a polar group having no proton, or the like.

Specific examples of the compound having an acidic group in the compound having an acidic group or a thermolatent acidic group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, and octanoic acid. , citric acid, citric acid, glycolic acid, glyceric acid, oxalic acid (also known as oxalic acid), malonic acid (also known as malonic acid), succinic acid (also known as succinic acid), Glutaric acid, adipic acid (also known as adipic acid), 1,2-cyclohexanedicarboxylic acid, 2-oxopropionic acid, 2-hydroxysuccinic acid, 2-hydroxypropanetricarboxylic acid, fluorenyl amber Acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanol, 1,2,3-trimethylpropane, 2,3,4-trimercapto-1-butanol, 2,4-didecyl- 1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, 1,5-dimercapto-3-thiapentane An aliphatic compound; benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methyl benzoate, dimethyl benzoate, trimethyl benzoate, 3-phenylpropionate, Dihydroxybenzoic acid, dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also known as o-benzene) Dicarboxylic acid), benzene-1,3-dicarboxylic acid (also known as isophthalic acid), benzene-1,4-dicarboxylic acid (also known as terephthalic acid), benzene-1,2,3- Tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzene hexacarboxylic acid, biphenyl-2,2'-dicarboxylic acid, 2-(carboxyl group) Benzoic acid, 3-(carboxymethyl)benzoic acid, 4-(carboxymethyl)benzoic acid, 2-(carboxycarbonyl)benzoic acid, 3-(carboxycarbonyl)benzoic acid, 4-(carboxycarbonyl)benzene Formic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, diphenolic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3- Dimercaptobenzene, 1,4-didecylbenzene, 1,4-naphthalene dithiol, 1,5-naphthalene dithiol, 2,6-naphthalene dithiol, 2,7-naphthalene dithiol, 1, 2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-nonyl(decylmethyl)benzene, 1,2,4-para ( Mercaptomethyl)benzene, 1,3,5-nonyl(decylmethyl)benzene, 1,2,3-nonyl(decylethyl)benzene, 1,2,4-nonyl(decylethyl)benzene, 1, An aromatic compound such as 3,5-paran (nonylethyl)benzene; nicotinic acid, isonicotinic acid, 2-furancarboxylic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, Pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid , imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-di a five-membered heterocyclic compound containing a nitrogen atom such as a carboxylic acid; thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-di Carboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5 -dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-indenyl- 1,2,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5- Dimercapto-1,3,4-thiadiazole, 3-(5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl)succinic acid, 2-(5-mercapto-1,3 , 4-thiadiazol-2-ylsulfanyl) succinic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio)acetic acid, (5-mercapto-1,3,4- Thiadiazol-2-yl Sulfur)acetic acid, 3-(5-mercapto-1,2,4-thiadiazol-3-ylthio)propionic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-ylsulfide Propionic acid, 3-(5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl)succinic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-ylsulfide Succinic acid, 4-(3-mercapto-1,2,4-thiadiazol-5-yl)thiobutanesulfonic acid, 4-(2-mercapto-1,3,4-thiadiazole-5- a five-membered heterocyclic compound containing a nitrogen atom and a sulfur atom such as thiobutanesulfonic acid; pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid , pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, 嗒井-3, 5-dicarboxylic acid, 嗒井-3,6-dicarboxylic acid, 嗒 well-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine- 4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6-di Carboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropylamino-4,6-dimercapto-s -triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimethyl- Nitrogen atom such as s-triazine Six heterocyclic compounds.

Among these, from the viewpoint of further improving the adhesion of the obtained resin film, the number of acidic groups in the compound having an acidic group is preferably two or more.

Moreover, in compounds having an acidic group or a thermolatent acidic group Specific examples of the compound having a thermolatent acidic group are, for example, compounds in which the acidic group of the compound having an acidic group is substituted with a thermolabile acidic group. For example, gindium (1-propoxyethyl) 1,2,4-benzenetricarboxylate obtained by substituting a carboxyl group of 1,2,4-benzenetricarboxylic acid with a blocked carboxylic acid group can be used. As a compound having a thermolabile acidic group. From the viewpoint of further improving the adhesion of the obtained gate insulating film, the number of the thermally latent acidic groups in the compound having a thermolatent acidic group is preferably two or more.

About 100 parts by weight of the cyclic polyolefin polymer (A), the hair The content of the compound having an acidic group or a thermolatent acidic group in the resin composition used in the present invention is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 45 parts by weight, still more preferably from 2 to 40 parts by weight. More preferably, it is in the range of 3 to 30 parts by weight. When the amount of the compound having an acidic group or a thermolabile acidic group is within the above range, the resin composition can be a resin composition excellent in liquid stability.

The preparation method of the resin composition used in the present invention is not particularly limited The components constituting the resin composition may be mixed by a known method.

The method of mixing is not particularly limited, and it is preferred to mix a solution or a dispersion obtained by dissolving or dispersing each component constituting the resin composition in a solvent. Thereby, the resin composition can be obtained in the form of a solution or a dispersion.

Dissolving or dispersing the components constituting the resin composition in a solvent The method can be carried out in accordance with the usual method. Specifically, it can be carried out by stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disperser, a planetary mixer, a twin-shaft mixer, a ball mill, a three-roller, or the like. Further, after dissolving or dispersing each component in a solvent, it can be filtered, for example, using a filter having a pore diameter of about 0.5 μm or the like.

(thin film transistor)

Next, the thin film transistor of the present invention will be described. The thin film transistor of the present invention has a gate insulating film composed of the above resin composition and a semiconductor layer formed on the gate insulating film, and the semiconductor layer is composed of at least one of In, Ga, and Zn. It is composed of a sputter film made of a crystalline oxide semiconductor. In the first drawing, a cross-sectional view of a thin film transistor 1 as an example of a thin film transistor of the present invention is shown. As shown in Fig. 1, the thin film transistor 1 has a gate electrode 3, a gate insulating film 4 made of the above resin composition, and a half on the substrate 2. The conductor layer 5, the source electrode 6 and the drain electrode 7 are the bottom gate contact plug type thin film transistors. Further, although a single thin film transistor is shown in FIG. 1, a configuration in which a plurality of thin film transistors 1 are formed on the substrate 2 (for example, an active array substrate or the like) may be employed. Further, the thin film transistor 1 shown in Fig. 1 is an example of the thin film transistor of the present invention. Hereinafter, the thin film transistor 1 shown in Fig. 1 will be described as an example, but the thin film electric device of the present invention is described. The crystal is not limited to the configuration shown in Fig. 1 .

The substrate 2 is not particularly limited, and examples thereof include flexibility of a flexible plastic such as polycarbonate, polyimide, polyethylene terephthalate or alicyclic olefin polymer. A substrate, a glass substrate such as quartz, soda glass or inorganic alkali glass, or a tantalum substrate such as a tantalum wafer.

The gate electrode is formed of a conductive material. Examples of the conductive material include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony, lead, antimony, indium, palladium, iridium, iridium, osmium, aluminum, lanthanum, cerium, molybdenum, and the like. Tungsten, tin oxide. Antimony, indium oxide. Tin (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon glue, lithium, barium, magnesium, potassium, calcium, barium, titanium, manganese, zirconium, gallium, germanium, sodium, Sodium-potassium alloy, magnesium/copper mixture, magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum mixture, lithium/aluminum mixture, aluminum/titanium mixture, molybdenum/titanium mixture, and the like. Further, examples of the known conductive polymer which enhances conductivity by doping or the like include conductive polyaniline, conductive polypyrrole, and conductive polythiophene (polyethylenedioxythiophene and polystyrene sulfonate). Acid complexes) and the like. Among these, preferred are chromium, molybdenum, aluminum/titanium mixtures and aluminum/titanium mixtures, more preferably chromium, aluminum/titanium mixtures and molybdenum/titanium mixtures, particularly preferably aluminum/titanium mixtures and molybdenum/titanium mixtures. The gate electrode 3 is, for example, the above conductivity A material is formed on the substrate 2 by sputtering, and then a etching process is performed to form a predetermined pattern on the substrate 2.

The gate insulating film 4 is composed of the above-described resin composition, and the resin composition is applied onto the substrate 2 on which the gate electrode 3 is formed in a predetermined pattern, and is formed by curing after removing the solvent. The coating method of the resin composition is, for example, various methods such as a spray coating method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a bar coating method, and a screen printing method. Further, the curing temperature is usually 100 to 300 ° C, more preferably 100 to 250 ° C, and even more preferably 100 to 150 ° C, and the hardening time is usually 0.5 to 300 minutes, preferably 1 to 150 minutes, more preferably 1 to 1 60 minutes. The thickness of the gate insulating film 4 is not particularly limited, but is preferably 100 to 400 nm, more preferably 100 to 300 nm, still more preferably 100 to 200 nm.

The semiconductor layer 5 is a sputtering film composed of an amorphous oxide semiconductor containing at least one of In, Ga, and Zn. The amorphous oxide semiconductor may be at least one element selected from the group consisting of In, Ga, and Zn, and examples thereof include zinc oxide (ZnO), indium zinc oxide (IZO), and zinc tin oxide ( ZTO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), indium gallium zinc oxide (IGZO), and the like.

The semiconductor layer 5 is usually formed by sputtering. Specifically, a target material made of a metal oxide forming the semiconductor layer 5 is sputtered to form a sputtering film made of a metal oxide (amorphous oxide semiconductor) on the surface of the gate insulating film 4. The thickness of the semiconductor layer 5 is preferably 10 to 100 nm, more preferably 20 to 80 nm, still more preferably 30 to 50 nm.

The source electrode 6 and the drain electrode 7 are formed of a conductive material. As the conductive material, the same material as the above-described gate electrode 3 can be used. The source electrode 6 and the drain electrode 7 are formed, for example, by sputtering on the semiconductor layer 5, and secondly, a predetermined pattern is formed on the semiconductor layer 5 by etching.

In the above, as a thin film transistor, a bottom gate contact plug type thin film transistor 1 as shown in Fig. 1 is exemplified, but a gate insulating film composed of the resin composition of the present invention is used. It is also applicable to the gate insulating film of the bottom gate contact plug type thin film transistor 1a shown in Fig. 2, and the thin film transistor 1a can also be obtained in the same manner as described above. In the thin film transistor 1a shown in FIG. 2, the same components as those of the above-described thin film transistor 1 are denoted by the same reference numerals, and their description will be omitted. In other words, the thin film transistor 1a shown in Fig. 2 has the gate electrode 3, the gate insulating film 4 composed of the resin composition, the source electrode 6, and the drain electrode 7 on the substrate 2, The semiconductor layer 5 is formed over the pole insulating film 4, the source electrode 6, and the drain electrode 7.

Alternatively, the gate insulating film composed of the resin composition of the present invention can be applied to the gate insulating film of the thin film transistor 1b of the etching stop layer type shown in Fig. 4 . Here, FIG. 4 is a cross-sectional view showing an etch stop layer type thin film transistor 1b including a gate insulating film formed of the resin composition of the present invention, and the same constituent members as the above-described thin film transistor 1 are attached. The number is omitted and its description is omitted. The thin film transistor 1b shown in FIG. 4 is formed with an etching stop 8 so as to cover the channel portion 9. In the thin film transistor 1b, the gate electrode 3, the gate insulating film 4 composed of the resin composition, and the semiconductor layer 5 are formed on the substrate 2 as shown in FIG. An etch stop 8 is formed on the layer 5 to cover the end of the semiconductor layer 5 and the etch stop 8 The source electrode 6 and the drain electrode 7 are individually provided in an end portion manner.

In the present invention, the gate insulating film 4 is composed of the above resin composition In the case of the resin composition, the cyclic polyolefin polymer (A) and the epoxy-based crosslinking agent (B) are contained, and the heat resistance and the plasma resistance are excellent. Therefore, in the case where the semiconductor layer 5 is formed on the gate insulating film 4, even if the gate insulating film 4 is exposed to a high temperature or a plasma to form a film by sputtering, the thermal deterioration of the gate insulating film 4 can be effectively prevented or The plasma is degraded. Therefore, a material having a higher carrier mobility than the organic semiconductor and an amorphous oxide semiconductor containing at least one of In, Ga, and Zn which are required to be formed by a sputtering method can be used as the semiconductor layer 5.

Therefore, according to the present invention, by being able to effectively prevent sputtering Degradation of the gate insulating film 4, the obtained thin film transistor can be excellent in on/off ratio and leakage current characteristics, and the semiconductor layer 5 can be formed of an amorphous oxide semiconductor having excellent carrier mobility. According to this, it is possible to provide a thin film transistor having a high mobility, a large on/off ratio, and a small leakage current.

Example

The present invention will be more specifically described below by way of examples and comparative examples. Parts and % in each case are on a weight basis unless otherwise noted.

Further, the definition of each characteristic and the evaluation method are as follows.

<mobility rate>

The electrical characteristics of the obtained thin film transistor were evaluated in a gas atmosphere and a dark room using a semiconductor parameter analyzer (manufactured by Agilent, Inc., 4156C). As a result, the obtained thin film transistor showed characteristics as a p-type crystal element. Then, the drain voltage Vd is fixed to Vd=10V, and the gate voltage (Vg) is changed from Vg=+20V to -20V, and is transmitted using a semiconductor parameter analyzer. Evaluation of characteristics. Further, the obtained thin film transistor has a saturated region, and in the present embodiment, the electric field effect mobility is obtained from the saturated region.

Further, for the calculation of the electric field effect mobility of the thin film transistor, the following formula is used. Also, the higher the mobility, the better.

Id=μCinW(Vg-Vth) ² /2L

(wherein Cin is the capacitance per unit area of the gate insulating film, W is the channel width, L is the channel length, Vg is the gate voltage, Id is the drain current, μ is the mobility, and Vth is the beginning of the channel formation. The threshold voltage of the gate.)

<on/off ratio>

For the obtained thin film transistor, a semiconductor tester (R6425 manufactured by Advantest Corporation) was used to test the current at the time of ON and the current at the time of OFF, and the ratios of these were calculated, thereby performing an on/off ratio (on/off current). Determination of the ratio). The higher the on/off ratio, the better. In the present embodiment, 1 × 10 ⁵ or more is good.

<leakage current>

The obtained thin film transistor is applied with a voltage of 20 V between the source electrode and the drain electrode in the atmosphere and in the dark room, and the voltage applied to the gate electrode is changed from +20 V to -20 V, and the source electrode and the drain electrode are The current flowing between the electrodes was measured with a manual probe and a semiconductor parameter analyzer (manufactured by Agilent, 4156C) to measure the leak current. The lower the leakage current, the better. In the present embodiment, 1 × 10 ^-12 or less is good.

Synthesis Example 1

<Preparation of cyclic olefin polymer (A-1)>

N-(2-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine 40 mol% and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] 12-9-ene 60 mole % of a monomer mixture consisting of 100 parts, 1,5-hexadiene 2 parts, (1,3-bis(2,4,6-trimethylbenzene) (Imidazoline-2-ylidene)(tricyclohexylphosphine)benzylidene hydrazine dichloride (synthesized as described in Org. Lett., Vol. 1, p. 953, 1999) 0.02 parts, and two 200 parts of ethylene glycol ethyl ether was placed in a glass pressure-resistant reactor which was replaced with nitrogen, and reacted at 80 ° C for 4 hours while stirring to obtain a polymerization reaction liquid.

Then, the obtained polymerization reaction liquid was placed in an autoclave, and stirred at 150 ° C under a hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction to obtain a polymer solution containing the cyclic olefin polymer (A-1). The obtained cyclic olefin polymer (A-1) had a polymerization conversion ratio of 99.7%, a polystyrene-equivalent weight average molecular weight of 7,150, a number average molecular weight of 4,690, a molecular weight distribution of 1.52, and a hydrogenation ratio of 99.7%. Further, the polymer solution of the obtained cyclic olefin polymer (A-1) had a solid content concentration of 34.4% by weight.

"Embodiment 1"

<Preparation of Resin Composition>

291 parts of a solution of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1 as a cyclic olefin polymer (A) (100 parts of a cyclic olefin polymer (A-1)) was mixed and dissolved as an epoxy Epoxidized butane tetracarboxylic acid ruthenium (3-cyclohexenylmethyl)-modified ε-caprolactone (trade name "EPOLEAD GT 401", manufactured by Daicel Chemical Industry Co., Ltd., having a ring type Epoxy-containing aliphatic cyclic tetra-functional epoxy resin, molecular weight (Mw) = 730) 30 parts, pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyl) as antioxidant Phenyl)propionate] (trade name "Irganox 1010", manufactured by BASF Corporation) 1.5 parts, an anthrone-based surfactant (product name "KP341", manufactured by Shin-Etsu Chemical Co., Ltd.) 0.03 as a surfactant After the mixture and 100 parts of ethylene glycol dimethyl ether as a solvent, it was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition.

<Manufacture of thin film transistor>

Next, the resin composition obtained above was used to obtain the thin film transistor 1 shown in Fig. 1. Further, Fig. 3 is a view showing a method of manufacturing the thin film transistor 1.

(1) pre-treatment

The glass substrate was prepared, and the prepared glass substrate was ultrasonically washed in pure water, air-dried, and baked at 100 ° C for 1 hour.

(2) Formation of gate electrode

Next, as shown in Fig. 3(A), an aluminum layer is formed by vacuum deposition on the glass substrate (substrate 2) subjected to the pretreatment, and the gate electrode 3 is formed by patterning the aluminum layer. Further, the thickness of the gate electrode 3 is 50 nm.

(3) Formation of gate insulating film

Next, the substrate 2 on which the gate electrode 3 is formed is placed on a spin coater, and a predetermined amount of the resin composition obtained above is dropped on the glass substrate 2, and the substrate 2 is rotated at a rotation speed of about 2000 rpm for 60 seconds. To form a coating film. Thereafter, the substrate 2 on which the coating film was formed was baked on the hot plate at a temperature of 150 ° C for about 60 minutes, whereby the gate insulating film 4 as shown in Fig. 3(B) was formed. Further, the thickness of the gate insulating film 4 is 200 nm.

(4) Formation of a semiconductor active layer

Next, as shown in Fig. 3(C), on the gate insulating film 4 of the substrate 2 on which the gate electrode 3 and the gate insulating film 4 are formed, indium gallium zinc is formed by a sputtering method at a thickness of 40 nm. Semiconductor formed by a sputtering film of oxide (IGZO) Layer 5. The sputter film of indium gallium zinc oxide (IGZO) is a sputtering apparatus (product name "CFS-4EP-LL", manufactured by Shibaura Mechatronics Co., Ltd.), and has an output of 300 W, an argon flow rate of 10 sccm, and an oxygen flow rate of 10 sccm in the presence of argon gas. The film was formed under the conditions of 0.6 Pa. Further, as a target of sputtering, indium gallium zinc oxide (IGZO) is used.

(5) Formation of source electrode and drain electrode

Next, on the semiconductor layer 5 on which the gate electrode 3, the gate insulating film 4, and the semiconductor layer 5 are formed, gold is deposited by vacuum evaporation, and the gold layer is patterned to form a source. The electrode 6 and the drain electrode 7 are used to obtain the thin film transistor 1 shown in Fig. 3(D). Further, the thickness of the source electrode 6 and the drain electrode 7 was 50 nm.

Then, using the obtained thin film transistor, mobility, Each evaluation of ON/OFF ratio and leakage current. The results are shown in Table 1.

<<Example 2》

In the preparation of the resin composition for forming the gate insulating film 4, in addition to the epoxidized butane tetracarboxylate (3-cyclohexenylmethyl) as the epoxy-based crosslinking agent (B), ε- The resin composition and the film transistor obtained in the same manner as in Example 1 were evaluated in the same manner except that the amount of the caprolactone was changed from 30 parts to 50 parts. The results are shown in Table 1.

Example 3

In the preparation of the resin composition for forming the gate insulating film 4, in addition to the epoxidized butane tetracarboxylate (3-cyclohexenylmethyl) as the epoxy-based crosslinking agent (B), ε- 30 parts of caprolactone, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct using 2,2-bis(hydroxymethyl)1-butanol (trade name) "EHPE3150", which is a 15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, and has a molecular weight (Mw) = 2234) and is substituted by 30 parts, and is the same as in the first embodiment. The obtained resin composition and the film transistor were evaluated in the same manner. The results are shown in Table 1.

Example 4

In the preparation of the resin composition for forming the gate insulating film 4, in addition to the epoxidized butane tetracarboxylate (3-cyclohexenylmethyl) modified ε-hex as the epoxy-based crosslinking agent (B) 30 parts of lactone, and further using 30 parts of 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)1-butanol, The resin composition and the film transistor were obtained in the same manner as in Example 1, and evaluated in the same manner. The results are shown in Table 1.

"Embodiment 5"

In the preparation of the resin composition for forming the gate insulating film 4, in addition to further using N, N, N', N', N", N"-(hexadecyloxy) as the melamine-based crosslinking agent (C) A resin composition and a film transistor obtained in the same manner as in Example 1 were evaluated in the same manner as in the case of a partial hydroxymethyl group-substituted product of melamine (trade name "CYMEL350", manufactured by Cytech Industries, Inc.). The results are shown in Table 1.

"Embodiment 6"

In the preparation of the resin composition for forming the gate insulating film 4, in addition to further using N, N, N', N', N", N"-(hexadecyloxy) as the melamine-based crosslinking agent (C) A resin composition and a film transistor obtained in the same manner as in Example 1 except for a partial methylol group substitution of melamine (trade name "CYMEL370", manufactured by Cytech Industries Co., Ltd.), and the same evaluation was carried out. price. The results are shown in Table 1.

Comparative Example 1

In the preparation of the resin composition for forming the gate insulating film 4, in addition to the epoxidized butane tetracarboxylic acid ruthenium (3-cyclohexenylmethyl) modified ε- not blended with the epoxy crosslinking agent (B) A resin composition and a film transistor were obtained in the same manner as in Example 1 except for caprolactone, and the same evaluation was carried out. The results are shown in Table 1.

Comparative Example 2

In the preparation of the resin composition for forming the gate insulating film 4, in addition to the epoxidized butane tetracarboxylic acid ruthenium (3-cyclohexenylmethyl) modified ε- not blended with the epoxy crosslinking agent (B) A resin composition and a film transistor were obtained in the same manner as in Example 5 except for caprolactone, and the same evaluation was carried out. The results are shown in Table 1.

Comparative Example 3

In the preparation of the resin composition for forming the gate insulating film 4, in addition to the epoxidized butane tetracarboxylic acid ruthenium (3-cyclohexenylmethyl) modified ε- not blended with the epoxy crosslinking agent (B) A resin composition and a film transistor were obtained in the same manner as in Example 6 except for caprolactone, and the same evaluation was carried out. The results are shown in Table 1.

Comparative Example 4

A thin film transistor was obtained in the same manner as in Comparative Example 1, except that the semiconductor layer 5 was formed by replacing the sputtering film of indium gallium zinc oxide (IGZO) with an a-Si layer (amorphous germanium layer), and the same evaluation was performed. Further, the a-Si layer (amorphous germanium layer) was formed to have a thickness of 100 nm using a chemical vapor deposition (CVD) apparatus (the same applies to Comparative Examples 5 and 6 to be described later). The results are shown in Table 1.

Comparative Example 5

In addition to the semiconductor layer 5, the indium gallium zinc oxide is replaced by an a-Si layer (amorphous germanium layer). A thin film transistor was obtained in the same manner as in Comparative Example 2 except that a sputtering film of the material (IGZO) was formed, and the same evaluation was carried out. The results are shown in Table 1.

Comparative Example 6

A thin film transistor was obtained in the same manner as in Comparative Example 3 except that the semiconductor layer 5 was formed by replacing the sputtering film of indium gallium zinc oxide (IGZO) with an a-Si layer (amorphous germanium layer), and the same evaluation was performed. The results are shown in Table 1.

As shown in Table 1, the gate insulating film 4 is composed of a cyclic olefin-containing polymer. The film of the composition (A) and the epoxy-based crosslinking agent (B) was formed, and the semiconductor layer 5 was formed using the sputtering film of indium gallium zinc oxide (IGZO), and the obtained film was obtained. The transistor is a thin film transistor having a high mobility, a large on/off ratio, and a small leakage current. In particular, in the first to sixth embodiments, the gate insulating film 4 is formed using a resin composition containing a cyclic olefin polymer (A) and an epoxy crosslinking agent (B). When the semiconductor layer 5 is formed, The deterioration of the gate insulating film due to the influence of heat or plasma generated during sputtering can be effectively suppressed, and the thin film transistor obtained thereby can have high mobility, large on/off ratio, and small leakage current. Thin film transistor. Further, in Examples 1 to 6, two types of Example 4 were used as the epoxy-based crosslinking agent (B), and the epoxy-based crosslinking agent (B) and the melamine-based crosslinking agent (C) were used in combination. In Examples 5 and 6, each of the characteristics of the mobility, the on/off ratio, and the leak current was particularly excellent.

On the other hand, the gate insulating film 4 does not contain epoxy crosslinking. In Comparative Examples 1 to 3 formed by the resin composition of the agent (B), the obtained film transistor was a film transistor having an on/off ratio and a leak current difference. Further, in Comparative Examples 1 to 3, the reason why the on/off ratio and the leak current are inferior is that the semiconductor layer 5 is formed by sputtering after the formation of the gate insulating film 4, which occurs during sputtering. The resin composition constituting the insulating film 4 is deteriorated by the influence of heat or plasma. Accordingly, it is considered that the insulation of the gate insulating film 4 is lowered.

Further, the gate insulating film 4 is formed using a resin composition not containing the epoxy-based crosslinking agent (B), and the semiconductor layer 5 is formed of an a-Si layer (amorphous germanium layer) in Comparative Examples 4 to 6. The obtained thin film transistor is a thin film transistor having low mobility, on/off ratio, and poor leakage current.

1‧‧‧film transistor

2‧‧‧Substrate

3‧‧‧gate electrode

4‧‧‧Gate insulation film

5‧‧‧Semiconductor layer

6‧‧‧Source electrode

7‧‧‧汲electrode

Claims (7)

A thin film transistor comprising a gate insulating film and a semiconductor layer formed on the gate insulating film, wherein the semiconductor layer is made of an amorphous oxide semiconductor containing at least one of In, Ga, and Zn The gate insulating film is composed of a cyclic olefin polymer (A) having a protic polar group and an epoxy group having two or more reactive groups with the protonic polar group in the molecule. The epoxy resin crosslinking agent (B) is composed of a resin composition. The thin film transistor according to the first aspect of the invention, wherein the content of the epoxy crosslinking agent (B) is 100 parts by weight based on 100 parts by weight of the cyclic olefin polymer (A). 10 to 100 parts by weight. The thin film transistor according to the first or second aspect of the invention, wherein the resin composition contains two or more different compounds as the epoxy-based crosslinking agent (B). The thin film transistor according to the third aspect of the invention, wherein the resin composition contains a compound having a molecular weight (Mw) of less than 1,000 and a compound having a molecular weight (Mw) of 1,000 or more as the epoxy-based crosslinking agent (B). The thin film transistor according to the third aspect of the invention, wherein the resin composition contains a compound having a terminal epoxy group and a compound having an alicyclic epoxy group as the epoxy crosslinking agent (B). The thin film transistor according to the first or second aspect of the invention, wherein the resin composition further contains a melamine crosslinking agent (C). The thin film transistor according to claim 6, wherein the resin composition has a weight of 100% based on the cyclic olefin polymer (A). The content of the melamine-based crosslinking agent (C) is 10 to 50 parts by weight.