JP2021055049A - Resin composition, and method for producing element using the same - Google Patents

Abstract

To provide a resin composition that can form an insulating layer with high dielectric constants and reduced leakage currents.SOLUTION: A resin composition at least has (a) polymer A: a polymer in which a polymer is bound to an inorganic particle having a hydroxy group on the surface, (b) polymer B: a polymer that is not bound to an inorganic particle and has a functional group capable of forming a hydrogen bond with a hydroxy group on the inorganic particle in the polymer A, and (C) a solvent.SELECTED DRAWING: None

Description

The present invention relates to a resin composition and a method for manufacturing an element using the resin composition.

In recent years, techniques for manufacturing electronic devices such as electronic paper, flexible sensors, and RFID (Radio Frequency Identification) tags by using a coating method have been studied. Since the vacuum process and the high temperature process can be avoided by using the coating method, the electronic device can be manufactured at low cost.

Electronic devices include elements such as field effect transistors (FETs) and capacitors. These elements require an insulating film that insulates the upper and lower electrodes.

The insulating film in the FET is a semiconductor layer, a source electrode, and a gate insulating film that separates the drain electrode and the gate electrode. The electrical characteristics, surface smoothness, and film thickness of the gate insulating film have a great influence on FET characteristics such as leakage current value and FET ON / OFF current value.

The insulating film in the capacitor is a dielectric film that separates the upper electrode and the lower electrode and accumulates the electric charge generated by the electric field applied between the upper and lower electrodes. The electrical characteristics, surface smoothness, and film thickness of the dielectric film have a great influence on the capacitor characteristics such as the leakage current value and the amount of accumulated charge.

As a material for an insulating film, an organic material soluble in an organic solvent such as an organic polymer is being energetically studied. These can form a low-cost thin film by a coating method such as slit coating, and can form a thin film on a film substrate such as polyethylene terephthalate by a low temperature process. In particular, in order to increase the dielectric constant of the insulating film, studies on adding an inorganic compound to the insulating film have been actively conducted.

Examples of the insulating film obtained by adding an inorganic compound to an organic polymer include a gate insulating film containing a polysiloxane chemically bonded to inorganic particles (see, for example, Patent Document 1), and a gate insulating film containing a polymer and inorganic oxide particles. (See, for example, Patent Document 2).

International Publication No. 2019/065561 Japanese Unexamined Patent Publication No. 2013-115162

However, it has been clarified that the technique described in Patent Document 1 has a problem that the film thickness unevenness of the insulating film in the vicinity of the lower electrode becomes large and the leakage current of the element becomes high. Further, Patent Document 1 does not mention a capacitor, and it has been found that the above problem is particularly remarkable in a capacitor having a large lower electrode area.

Further, as a result of examining the technique of Patent Document 2, the present inventor has revealed that although the thickness unevenness of the insulating film is small, the leakage current of the capacitor becomes large due to the formation of the conductive path by some agglomerated inorganic particles. Became.

Focusing on the above problems, it is an object of the present invention to provide a resin composition capable of forming an insulating layer having a high dielectric constant and a reduced leakage current.

The present inventor presumed that the cause of the uneven film thickness in the vicinity of the electrode in the technique of Patent Document 1 was the low fluidity of the polymer chemically bonded to the inorganic particles, and investigated the present invention. I arrived.

That is, the present invention is at least (a) polymer A: a polymer in which a polymer is bonded to inorganic particles having a herodoxy group on the surface, and (b) polymer B: a polymer that is not bonded to inorganic particles and is contained in the polymer A. It is a resin composition containing a polymer having a functional group capable of forming a hydrogen bond with a hydroxy group on the surface of an inorganic particle, and (c) a solvent.

According to the device of the present invention, a resin composition capable of forming an insulating film having a high film thickness uniformity in the vicinity of the electrode and on the electrode can be obtained, and as a result, a high dielectric constant and a low leakage current of the insulating film can be obtained. It is possible to obtain compatible elements.

Schematic cross-sectional view showing an example of a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a capacitor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a capacitor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a capacitor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a capacitor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a circuit obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a circuit obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a circuit obtained by using the resin composition of the present invention. Block diagram showing an example of a wireless communication device using a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a capacitor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a field effect transistor obtained by using the resin composition of the present invention. Schematic cross-sectional view showing an example of a circuit obtained by using the resin composition of the present invention.

Hereinafter, preferred embodiments of the resin composition according to the present invention and the method for producing an element using the resin composition will be described in detail. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented according to an object and an application.

<Resin composition>
The resin composition of the present invention has at least (a) polymer A: a polymer in which a polymer is bonded to inorganic particles having a herodoxy group on the surface, and (b) polymer B: a polymer that is not bonded to inorganic particles and the polymer A. It is a resin composition containing (c) a polymer having a functional group capable of forming a hydrogen bond with a hydroxy group on the surface of the inorganic particles contained in the above.

(Polymer A: Polymer to which inorganic particles having a herodoxy group are bonded to the surface)
"Bond" in "polymer with inorganic particles" means covalent bond, ionic bond, coordination bond, metal bond, hydrogen bond, bond by π-π interaction, bond by ion-dipole interaction, dipole. Bonds by -dipole interaction, dipole-induced dipole interaction, hydrophobic interaction, charge transfer complex formation, metal-ligand complex formation, London dispersive bond, And a bond selected from van der Waals forces.

The inorganic particles have a functional group that can react with the polymer, such as a hydroxy group, on the surface thereof, and the inorganic particles react with the polymer from there as a base point, and the inorganic particles are incorporated into the polymer. In the state where the inorganic particles are bound to the polymer, the aggregation of the inorganic particles in the solution state is suppressed as compared with the case where the inorganic particles and the polymer are mixed. Further, in a state where the inorganic particles are bonded to the polymer, the alkali solubility of the inorganic particles is improved, so that a cured film obtained from the resin composition of the present invention (hereinafter, unless otherwise specified, simply referred to as a "cured film"). Refers to a cured film obtained from the resin composition of the present invention), which can suppress a decrease in pattern processability due to residue generation. The "bond" is preferably a covalent bond from the viewpoint of agglutination suppression and pattern processability.

The presence or absence of bonding between the inorganic particles and the polymer can be confirmed by combining analytical means such as ¹³ C-NMR, ^{29 Si-NMR and IR.} For example, ¹³ C-NMR or ²⁹ Si-NMR is used to compare the spectrum of the inorganic particles, the spectrum of the polymer, and the spectrum of the polymer to which the inorganic particles are bonded. In the polymer to which the inorganic particles are bonded, the peak derived from the C or Si atom bonded to the inorganic particles is a peak having a chemical shift that does not exist in the spectrum of the polymer. Can be confirmed.

Similarly, in IR, the peak derived from the C or Si atom in the polymer to which the inorganic particles are bonded becomes a peak having a wave number different from the spectrum of the polymer, so it is possible to confirm the presence or absence of the bond between the inorganic particles and the polymer. it can.

(Inorganic particles)
The inorganic particles are not particularly limited as long as they are particles made of an inorganic substance. Since the inorganic particles have a small shrinkage rate during thermosetting, the generation of shrinkage stress can be suppressed. Therefore, the crack resistance of the cured film obtained from the resin composition of the present invention is improved, and the leakage current can be reduced.

As the inorganic particles, particles composed of a metal compound or a metalloid compound are preferable, and inorganic oxide particles are particularly preferable from the viewpoint of reactivity with a polymer.

Examples of the metal or semi-metal include elements selected from the group consisting of silicon, magnesium, calcium, strontium, barium, lanthanum, cerium, tin, titanium, zirconium, hafnium, yttrium, niobium, tantalum and aluminum. Examples of the metal compound or metalloid compound include the above-mentioned metal or metalloid halides, oxides, nitrides, hydroxides, carbonates, sulfates, nitrates or metasilicates.

The shape of the inorganic particles is not particularly limited, but in order to keep the surface of the cured film smooth, a shape having a low aspect ratio is preferable, and a spherical shape is more preferable.

From the viewpoint of suppressing aggregation of inorganic particles in a solution state and reducing leakage current by improving crack resistance of the cured film, the number average particle size of the inorganic particles is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 15 nm or more. It is preferable, and 20 nm or more is particularly preferable. On the other hand, the number average particle size is preferably 100 nm or less, more preferably 70 nm or less, further preferably 60 nm or less, and particularly preferably 50 nm or less. When the number average particle size is within the above range, the pattern processability of the cured film can be improved.

Here, the number average particle diameter of the inorganic particles can be determined by measuring as follows using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The cross section of the cured film is observed at a magnification of 50,000 to 200,000 times. When the inorganic particle is a true sphere, the diameter of the true sphere is measured and used as the particle size of the particle. When the inorganic particles are not true spheres, the longest diameter (hereinafter, "major axis diameter") and the longest diameter in the direction orthogonal to the major axis diameter (hereinafter, "minor axis diameter") are measured, and the major axis diameter and the shortest are measured. The biaxial average diameter obtained by averaging the shaft diameters is defined as the particle diameter of the particles. This particle size measurement is performed on 20 or more randomly selected particles, and the arithmetic mean thereof is taken as the number average particle size.

Examples of the inorganic particles used in the present invention include known particles such as those described in International Publication No. 2019/065561. Among them, from the viewpoint of high dielectric constant of the cured film, tin oxide-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, titanium oxide particles, zirconium oxide particles, hafnium oxide particles, yttrium oxide particles, niobium oxide particles, and tantalum oxide. Particles, tin oxide particles, tin oxide-zinc oxide composite particles, silicon oxide-zinc oxide composite particles, aluminum oxide particles, barium titanate particles, strontium titanate particles and barium titanate-strontium titanate composite particles, zirconic acid titanate Inorganic particles selected from lead particles, strontium titanate lead particles, strontium titanate bismuth particles, strontium titanate bismuth particles, and bismus strontium titanate particles are more preferable, and tin oxide- Titanium oxide-containing particles such as titanium oxide composite particles, silicon oxide-titanium oxide composite particles, and titanium oxide particles are particularly preferable. By improving the dielectric constant of the cured film, the element characteristics of the element obtained by using the resin composition of the present invention are improved. For example, in the case of FET, the current flowing on the circuit rises when the FET is driven (on) at a certain gate voltage value.

(polymer)
In the polymer A, the polymer is preferably soluble in a solvent. The skeleton of the polymer may be linear, cyclic or branched. Further, it is preferable that a crosslinkable functional group, a polar functional group, or a functional group that controls various properties of the polymer is introduced into the side chain. By using a polymer having these characteristics controlled, for example, coatability, surface flatness, solvent resistance, transparency, and good wettability of other inks can be obtained in the manufacturing process of the FET element. Further, it is possible to obtain a good FET element having excellent durability and stability after forming the FET element.

The polymer used in the present invention is not particularly limited as long as it exhibits insulating properties to the extent that the FET functions normally. For example, polysiloxane, polyamide, polyamideimide, polyimide, polybenzimidazole, polyvinyl alcohol, and polyvinyl. Phenol, polyacetal, polycarbonate, polyallylate, polyphenylene sulfide, polyethersulfone, polyetherketone, polyphthalamide, polyethernitrile, polymethylmethacrylate, polymethacrylicamide, polyvinylidene fluoride, polytetrafluoroethylene, polystyrene, polyester, aromatic Group polyether, novolak resin, phenol resin, acrylic resin, olefin resin, alicyclic olefin resin, vinyl chloride resin, epoxy resin, melamine resin, urea resin and the like can be used. Further, those obtained by copolymerizing or mixing other polymers with these polymers can also be used. Of these, polysiloxane is preferably used from the viewpoint of improving the on-current of the FET and reducing the leakage current.

The polysiloxane preferably has a structural unit represented by the general formula (1).

The polysiloxane having the structural unit represented by the general formula (1) can also be represented as a polysiloxane having the structural unit represented by the general formula (8).

In the general formulas (1) and (8), R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group or an alkenyl group. R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group or a silyl group. m represents 0 or 1. A ¹ represents an organic group containing at least two carboxyl groups, sulfo groups, thiol groups, phenolic hydroxyl groups or derivatives thereof. However, when the derivative has a cyclic condensation structure consisting of two of the carboxyl group, the sulfo group, the thiol group and the phenolic hydroxyl group, A ¹ represents an organic group having at least one of the cyclic condensation structures.

The alkyl group indicates a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group, and has a substituent. You may or may not have it. The substituent is not particularly limited, and examples thereof include an alkoxy group, an aryl group, and a heteroaryl group. These substituents may further have a substituent. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, and more preferably 1 or more and 8 or less, from the viewpoint of availability and cost.

The cycloalkyl group indicates, for example, a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group, and may or may not have a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an aryl group, and a heteroaryl group. These substituents may further have a substituent. The description of these substituents is also common to the following description. The number of carbon atoms of the cycloalkyl group is not particularly limited, but is preferably in the range of 3 or more and 20 or less.

The heterocyclic group refers to a group derived from an aliphatic ring having an atom other than carbon such as a pyran ring, a piperidine ring, and an amide ring in the ring, and has or does not have a substituent. May be good. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The aryl group indicates, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, an anthrasenyl group, a phenanthryl group, a terphenyl group, a pyrenyl group, and has or does not have a substituent. You may. The number of carbon atoms of the aryl group is not particularly limited, but is preferably in the range of 6 to 40.

The heteroaryl group refers to an aromatic group having one or more atoms other than carbon in the ring, such as a furanyl group, a thiophenyl group, a benzofuranyl group, a dibenzofuranyl group, a pyridyl group, and a quinolinyl group, and is a substituent. May or may not have. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably in the range of 2 to 30.

The alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, and may or may not have a substituent. The carbon number of the alkenyl group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

Further, the alkoxy group mentioned above as a substituent indicates a functional group in which one of the ether bonds is substituted with an aliphatic hydrocarbon group, for example, a methoxy group, an ethoxy group, a propoxy group, and the aliphatic hydrocarbon group is a functional group. It may or may not have a substituent. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 or more and 20 or less.

The organic group in A ¹ represents the above-mentioned alkyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group or alkenyl group. Of these, from the viewpoint of low hysteresis, an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group are preferable, an alkyl group and an aryl group are more preferable, and an alkyl group is further preferable.

Formula (1) or polysiloxane having the structural unit represented by (8), a carboxyl group as A ^1, containing sulfo groups, thiol group, phenolic hydroxyl group or at least two organic group containing derivatives thereof As a result, a solution containing an organic semiconductor such as pentacene or a polythiophene derivative or a semiconductor such as CNT can be smoothly applied onto the cured film, and a uniform semiconductor layer can be formed. It is presumed that this is because these polar functional groups present in the cured film can control the wettability of the semiconductor solution and enable repelling-free coating.

Further, the derivative is the carboxyl group, a sulfo group, if a two by cyclocondensation structure of thiol group and phenolic hydroxyl group containing at least one having an organic group the cyclocondensation structure as A ¹ Therefore, the same effect can be obtained.

In general formula (1) or polysiloxane having the structural unit represented by (8), that it has a A ^1, crack resistance of the cured film is increased, the reduction of the leakage current of the element Made.

Moreover, the general formula (1) or polysiloxane having the structural unit represented by (8), that it has a A ^1, during lithography of the cured film exhibits excellent solubility in an alkali developing solution. As a result, the pattern can be processed with high accuracy according to the design dimensions, so that the resolution is improved. The resolution is preferably 30 μm or less, more preferably 15 μm or less, and even more preferably 5 μm or less.

Among the derivatives of carboxyl group, sulfo group, thiol group or phenolic hydroxyl group, the acyclic condensed structure includes carboxylic acid ester with hydrocarbon group or silyl group, sulfonic acid ester, thioester, thioether and phenyl ether. Can be mentioned. In addition, carboxylic acid anhydrides and amide compounds or imide compounds produced by the reaction of carboxylic acid anhydrides with amine compounds can be mentioned.

Here, the silyl group is not particularly limited as long as it is a functional group having a Si atom as a bond point, and may have a hydrogen group, an organic group, and a silyl group, and may be mediated by an oxygen atom. Polysiloxane is also possible.

Examples of the cyclic condensation structure consisting of two of a carboxyl group, a sulfo group, a thiol group and a phenolic hydroxyl group include a cyclic acid anhydride structure, a cyclic ester structure, a cyclic thioester structure, a cyclic ether structure and a cyclic thioether structure.

Condensation includes both intraself and intermolecular condensation. In the case of condensation between other molecules, both polysiloxanes and those derived from other constituent materials are included.

The A ¹ in the general formula (1) and (8), the coating of the semiconductor solution improves, and from the viewpoint of reducing leakage current of the device according to the crack resistance improvement of the cured film, at least two carboxyl groups or derivatives thereof, Alternatively, an organic group having at least one cyclic acid anhydride group is preferable. As A ¹ , a group represented by the general formula (2) or (3) is more preferable.

In the general formula (2), X ¹ represents a single bond, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms. R ³ and R ⁴ independently represent a hydrogen atom, an organic group or a silyl group, respectively. In the general formula (3), X ² represents a single bond, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms.

In polysiloxane, the content ratio of the structural unit represented by the general formula (1) or (8) to the total silane structural unit is the leakage of the element due to the improvement of the coatability of the semiconductor solution and the crack resistance of the cured film. From the viewpoint of reducing the current and improving the resolution during lithography of the cured film, 0.5 mol% or more is preferable, 1.0 mol% or more is more preferable, and 1.5 mol% or more is further preferable. Further, from the viewpoint of preventing an increase in leakage current due to moisture absorption, 25 mol% or less is preferable, 20 mol% or less is more preferable, and 15 mol% or less is further preferable.

The content ratio of the structural unit represented by the general formula (1) or (8) in the total silane structural unit in the polysiloxane can be determined by ^{13 C-NMR.} In the carboxyl group and its derivative, the carbon atom of carbonyl is around 170-180 ppm of chemical shift, in the sulfo group and its derivative, the carbon atom bonded to the S atom is around 30-40 ppm of chemical shift, and in the thiol group and its derivative, it is around 30-40 ppm. The carbon atom bonded to the S atom is in the vicinity of the chemical shift of 10-20 ppm, and in the phenolic hydroxyl group and its derivative, the carbon atom in the aromatic ring bonded to the O atom derived from the phenolic hydroxyl group is in the vicinity of the chemical shift of 140-170 ppm, respectively. Appears characteristically. The content ratio of the structural unit can be obtained from the peak area ratio with the carbon atom in these and other structural units.

Examples of the structural units represented by the general formulas (1) and (8) include the following structural units derived from silane compounds.

As having a carboxyl group or a derivative thereof, dimethoxymethylsilylmethylsuccinic acid, diethoxymethylsilylmethylsuccinic acid, dimethoxyphenylsilylmethylsuccinic acid, diethoxyphenylsilylmethylsuccinic acid, trimethoxysilylmethylsuccinic acid, triethoxy Cyrilmethylsuccinic acid, 2-dimethoxymethylsilylethylsuccinic acid, 2-diethoxymethylsilylethylsuccinic acid, 2-dimethoxyphenylsilylethylsuccinic acid, 2-diethoxyphenylsilylethylsuccinic acid, 2-trimethoxysilylethylsuccinic acid Acid, 2-triethoxysilylethyl succinic acid, 3-dimethoxymethylsilylpropyl succinic acid, 3-diethoxymethylsilylpropylsuccinic acid, 3-dimethoxyphenylsilylpropylsuccinic acid, 3-diethoxyphenylsilylpropylsuccinic acid, 3 -Trimethoxysilylpropyl succinic acid, 3-triethoxysilylpropyl succinic acid, 4-dimethoxymethylsilylbutylsuccinic acid, 4-diethoxymethylsilylbutylsuccinic acid, 4-dimethoxyphenylsilylbutylsuccinic acid, 4-diethoxyphenyl Cyrilbutylsuccinic acid, 4-trimethoxysilylbutylsuccinic acid, 4-triethoxysilylbutylsuccinic acid, 5-dimethoxymethylsilylpentylsuccinic acid, 5-diethoxymethylsilylpentylsuccinic acid, 5-dimethoxyphenylsilylpentylsuccinic acid , 5-Diethoxyphenylsilylpentylsuccinic acid, 5-trimethoxysilylpentylsuccinic acid, 5-triethoxysilylpentylsuccinic acid, 6-dimethoxymethylsilylhexylsuccinic acid, 6-diethoxymethylsilylhexylsuccinic acid, 6- Dimethoxyphenylsilylhexyl succinic acid, 6-diethoxyphenylsilylhexyl succinic acid, 6-trimethoxysilylhexyl succinic acid, 6-triemethoxysilylhexyl succinic acid, anhydrides of compounds having these succinic acid structures, and these succinic acids. Examples thereof include structural units derived from compounds in which succinic acid is succinic acid.

As having a sulfo group or a derivative thereof, 5-dimethoxymethylsilylpentane-1,2-disulfonic acid, 5-diethoxymethylsilylpentane-1,2-disulfonic acid, 5-dimethoxyphenylsilylpentane-1,2. -Disulfonic acid, 5-diethoxyphenylsilylpentane-1,2-disulfonic acid, 5-trimethoxysilylpentane-1,2-disulfonic acid, 5-triethoxysilylpentane-1,2-disulfonic acid and their methyls. Examples include structural units derived from t-butyl esters in addition to esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters and sec-butyl esters.

As those having a thiol group or a derivative thereof, 3- (3-dimethoxymethylsilylpropyroxy) propane-1,2-dithiol, 3- (3-diethoxymethylsilylpropyroxy) propane-1,2-dithiol, 3- (3-Dimethoxyphenylsilylpropyroxy) propane-1,2-dithiol, 3- (3-diethoxyphenylsilylpropyroxy) propane-1,2-dithiol, 3- (3-trimethoxysilylpropyroxy) Propane-1,2-dithiol, 3- (3-triethoxysilylpropyroxy) propane-1,2-dithiol and their methylthioethers, ethylthioethers, n-propylthioethers, isopropylthioethers, n-butylthioethers, sec- Butylthioether In addition, structural units derived from t-butylthioether can be mentioned.

As having a phenolic hydroxyl group or a derivative thereof, 3-dimethoxymethylsilylpropyl group, 3-diethoxymethylsilylpropyl group, 3-dimethoxyphenylsilylpropyl group, 3-diethoxyphenylsilylpropyl group, 3-trimethoxy Catecol, resorcinol, hydroquinone or fluoroglucolcinol having a silylpropyl group or 3-triethoxysilylpropyl group, and their methyl ethers, ethyl ethers, n-propyl ethers, isopropyl ethers, n-butyl ethers, sec-butyl ethers plus t -Structural units derived from butyl ether can be mentioned.

1-carboxy-2-sulfo-5-trimethoxysilylpentane, 1-carboxyl as one containing one different type of group from each of a carboxyl group, a sulfo group, a thiol group, a phenolic hydroxyl group or a derivative thereof. -2-Mercapto-5-trimethoxysilylpentane, 1-sulfo-2-mercapto-5-trimethoxysilylpentane, 1-carboxy-2-hydroxy-4-trimethoxysilylbenzene, 1-sulfo-2-hydroxy- 4-Trimethoxysilylbenzene, 1-mercapto-2-hydroxy-4-trimethoxysilylbenzene and position isomers with different positions of these substituents, plus their methyl (thio) ester, ethyl (thio) ester, n -Propyl (thio) ester, isopropyl (thio) ester, n-butyl (thio) ester, sec-butyl (thio) ester, t-butyl (thio) ester, methyl (thio) ether, ethyl (thio) ether, n Derived from -propyl (thio) ether, isopropyl (thio) ether, n-butyl (thio) ether, sec-butyl (thio) ether, t-butyl (thio) ether, cyclic (thio) ester and cyclic (thio) ether Among the structural units, at least two carboxyl groups or derivatives thereof, or cyclic acid anhydride groups are used from the viewpoint of improving the coatability of the semiconductor solution and reducing the leakage current of the element by improving the crack resistance of the cured film. A structural unit derived from a silane compound having at least one is preferable, and a structural unit derived from a silane compound having a succinic acid, a succinic acid anhydride structure or a derivative thereof is more preferable, and a silane compound having a succinic acid or a succinic acid anhydride structure is derived. The structural unit of is more preferred. Specifically, 3-dimethoxymethylsilylpropyl succinic acid, 3-diethoxymethylsilylpropyl succinic acid, 3-dimethoxyphenylsilylpropyl succinic acid, 3-diethoxyphenylsilylpropyl succinic acid, 3-trimethoxysilylpropyl succinic acid. Structural units derived from acids, 3-triethoxysilylpropyl succinic acid and their anhydrides are more preferred, with structural units derived from 3-trimethoxysilylpropyl succinic acid, 3-triethoxysilylpropyl succinic acid and their anhydrides. Especially preferable.

The polysiloxane in the cured film preferably contains one or more structural units other than the general formulas (1) and (8) from the viewpoint of achieving both high insulation and crack resistance. Here, the insulating property in the present invention is an index of electricity through difficulty refers to volume resistivity is 10 ⁸ Ω · cm or more.

Examples of the structural unit other than the general formulas (1) and (8) include known ones such as those described in International Publication No. 2019/065561.

(Manufacturing method of polymer A)
Polymer A can be obtained, for example, by the following method. Here, the case of polysiloxane is taken as an example. After putting all the silane compounds and inorganic particles into the solvent, the mixture is stirred, an acid catalyst and water are added thereto over 1 to 180 minutes, and then the hydrolysis reaction is carried out at 15 to 80 ° C. for 1 to 180 minutes. The temperature during the hydrolysis reaction is more preferably 15 to 55 ° C. The obtained reaction solution is further heated at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours to carry out a condensation reaction, whereby a polysiloxane to which inorganic particles are bonded can be obtained. As described above, a method of hydrolyzing the silane compound and dehydrating and condensing it in the presence of inorganic particles can be mentioned.

Various conditions in the hydrolysis reaction are set in consideration of the reaction scale, the size and shape of the reaction vessel, for example, the acid concentration, the reaction temperature, the reaction time, etc., so that the physical properties suitable for the intended use can be obtained. Obtainable.

Acid catalysts used in the hydrolysis reaction of silane compounds include formic acid, oxalic acid, hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, and acids such as ion exchange resins. Examples include catalysts. The content of the acid catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total silane compound which is the raw material of the polysiloxane. The content of the acid catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. When the content of the acid catalyst is 0.05 parts by mass or more, the hydrolysis reaction proceeds sufficiently, and when it is 10 parts by mass or less, a rapid reaction can be suppressed.

Since the polysiloxane does not preferably contain the above acid catalyst from the viewpoint of storage stability, the catalyst may be removed after the hydrolysis reaction. As a method for removing the catalyst, water washing or treatment with an ion exchange resin is preferable from the viewpoint of ease of operation and removability. Here, the water washing refers to a method in which a solution of polysiloxane is diluted with an appropriate hydrophobic solvent, washed with water several times, and the obtained organic layer is concentrated with an evaporator or the like. The treatment with an ion exchange resin refers to a method in which the obtained polysiloxane solution is brought into contact with the ion exchange resin.

As the solvent used in the hydrolysis reaction, an organic solvent is preferable, and alcohols such as ethanol, propanol, butanol, 3-methyl-3-methoxy-1-butanol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl Ethers such as ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethyl ether; ketones such as methyl isobutyl ketone and diisobutyl ketone; amides such as dimethylformamide and dimethylacetamide; ethyl acetate, ethyl cellosolve acetate, 3-methyl Acetates such as -3-methoxy-1-butanol acetate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane and cyclohexane, as well as γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like. be able to. The amount of the solvent is preferably in the range of 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the total silane compound which is a raw material of polysiloxane. If it is 50 parts by mass or more, a rapid reaction can be suppressed, and if it is 500 parts by mass or less, hydrolysis can be sufficiently proceeded.

Further, as the water used for hydrolysis, ion-exchanged water is preferable. The amount of water can be arbitrarily selected, but when a silane compound having a hydrolyzing structure such as an acid anhydride group or an epoxy group is used in addition to the alkoxy group and the equivalent molar amount of water in the silane compound, it is used. It is advisable to further add hydrolyzable functional groups and equivalent molars or more of water. It is also possible to reheat or add a base catalyst in order to increase the degree of polymerization of the polysiloxane.

It is determined that the polysiloxane contains the structural unit represented by the general formula (1) or (8) by using one or a plurality of various organic analysis methods such as elemental analysis, nuclear magnetic resonance analysis, and infrared spectroscopic analysis. be able to.

(Polymer B: A polymer that is not bonded to the inorganic particles and has a functional group capable of forming a hydrogen bond with the hydroxy group on the surface of the inorganic particles contained in the polymer A)
When the polymer contained in the resin composition is only polymer A, the film thickness unevenness of the cured film of the resin composition formed around the lower electrode and on the lower electrode becomes large. For this reason, in the case of FET, the uneven film thickness of the gate insulating film becomes large, the element does not operate due to gate leak in the place where the film thickness is thin, and the on-current becomes low in the place where the film thickness is thick. There is a decline. Further, due to the uneven film thickness, in a substrate provided with a plurality of FETs, the variation in element characteristics within the substrate becomes large. On the other hand, in the case of a capacitor, if the area of the lower electrode is large and the film thickness unevenness of the cured film of the resin composition on the electrode becomes large, leakage may occur at the thin film thickness, and the yield of element formation becomes extremely low. .. Further, due to the uneven film thickness, the variation in element characteristics such as the capacitance value in the substrate becomes large.

It is presumed that the film thickness unevenness is caused by the low liquid fluidity of the polymer A when it is applied to the varnish or when it is dried, and the leveling property in the vicinity of the lower electrode is poor. It is presumed that the cause of this is that the polymer A contains inorganic particles. Therefore, it was found that when the polymer B was added in order to improve the liquid fluidity of the varnish of the polymer A, the above-mentioned film thickness unevenness was improved.

The polymer B is not particularly limited as long as it has a functional group capable of hydrogen bonding with the hydroxy group on the surface of the inorganic particles contained in the polymer A, and is polysiloxane, polyamide, polyamideimide, polyimide, polybenzimidazole, or polyvinyl alcohol. , Polyhydroxystyrene, polyacetal, polycarbonate, polyallylate, polyphenylene sulfide, polyethersulfone, polyetherketone, polyphthalamide, polyethernitrile, polymethylmethacrylate, polymethacrylicamide, aromatic polyether, novolak resin, phenol resin, Various polymers such as acrylic resin, epoxy resin, melamine resin, and urea resin can be used. Further, those obtained by copolymerizing or mixing other polymers with these polymers can also be used.

When a polymer having no functional group capable of hydrogen bonding with the hydroxy group on the surface of the inorganic particles contained in the polymer A is used, the dispersibility of the polymer A in the varnish is lowered and the inorganic particles are precipitated. , A uniform film cannot be obtained.

As the polymer B, a polymer having at least one functional group is preferable from the group consisting of a carboxyl group, a sulfo group, a phosphoric acid group, a mercapto group, a hydroxyl group, an epoxy group and derivatives thereof. In particular, from polysiloxane having a structural unit represented by the general formula (4), a resin having a phenolic hydroxyl group, polyester having a carboxylic acid residue represented by the general formula (5), and polymaleic acid and its derivatives. At least one selected from the group is preferred.

The polysiloxane having the structural unit represented by the general formula (4) can also be represented as a polysiloxane having the structural unit represented by the general formula (9).

In the general formulas (4) and (9), R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group or an alkenyl group. R ⁶ represents a hydrogen atom, an alkyl group, a cycloalkyl group or a silyl group. n represents 0 or 1. A ² represents an organic group containing at least one carboxyl group, sulfo group, thiol group, phenolic hydroxyl group, epoxy group or a derivative thereof. However, when the derivative has a cyclic condensation structure consisting of any two of the carboxyl group, sulfo group, thiol group and phenolic hydroxyl group, A ² has an organic group having at least one cyclic condensation structure. Represent.

Among the structural units represented by the general formulas (4) and (9), the same structural units as those described in the general formulas (1) and (8) can be used as the structural unit derived from the silane compound containing a carboxyl group. ..

Structural units represented by the general formulas (4) and (9), which have a sulfo group or a derivative thereof, a thiol group or a derivative thereof, a phenolic hydroxyl group or a derivative thereof, and a carboxyl group. As a group containing one different type of group from each of a group, a sulfo group, a thiol group, a phenolic hydroxyl group or a derivative thereof, the same ones as those in the above general formulas (1) and (8) may be used. it can.

Among the structural units represented by the general formulas (4) and (9), the structural units derived from the silane compound containing an epoxy group include β-glycidoxyethyl trimethoxysilane and β-glycidoxyethyl triethoxysilane. , Γ-Glysidoxypropyltrimethoxysilane, γ-Glysidoxypropyltriethoxysilane, γ-Glysidoxypropylmethyldimethoxysilane, γ-Glysidoxypropylphenyldimethoxysilane, γ-Glysidoxypropylcyclohexyldimethoxysilane , 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 2- (3,4-epylcyclohexyl) ethyltriethoxysilane, 2- (3,4-epylcyclohexyl) ethylmethyldimethoxysilane, 2- (3) , 4-Epylcyclohexyl) Ethylphenyldimethoxysilane, 2- (3,4-epylcyclohexyl) ethylcyclohexyldimethoxysilane, and other structural units derived from silane compounds.

Examples of the resin having a phenolic hydroxyl group include polyhirodoxystyrene and a phenol resin. The phenolic resin is a general monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, a phenol novolac resin and a cresol novolac. Novolac resin such as resin, naphthol novolac resin; polyfunctional phenol resin such as triphenol methane type phenol resin; modified phenol resin such as terpen-modified phenol resin and dicyclopentadiene-modified phenol resin; phenylene skeleton and / or biphenylene skeleton Examples thereof include an aralkyl type resin having a phenol aralkyl resin, phenylene and / or a naphthol aralkyl resin having a biphenylene skeleton.

In the general formula (5), R ⁷ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group, an alkenyl group, or an organic group represented by the general formula (6).

In the general formula (6), R ⁸ represents a hydroxyl group, an alkoxy group, or a functional group represented by the general formula (7).

In the general formula (7), R ⁹ represents a functional group represented by an alkylene group or an oxyalkylene group. However, at least one ester bond, amide bond, or urethane bond may be contained in the alkylene group and the oxyalkylene group. R ¹⁰ represents a hydrogen atom or a methyl group.

Having an unsaturated bond as in the general formula (7) enables an addition reaction between them and / or an acrylic group and / or a methacrylic group contained in a radically polymerizable compound described later, and as a result, between the polymers. By forming a crosslinked structure, the insulating film is densified, and crack resistance and solvent resistance are improved.

Examples of the polyester material having a carboxylic acid residue represented by the general formula (5) include WR-301 (manufactured by ADEKA Corporation), V-259ME (trade name) (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). Examples thereof include Findick M-8842, Findick M-8843, Findick M-8860, and Findick M-8961 (manufactured by DIC Corporation). These may be used alone or in combination of two or more.

The polyester material having a carboxylic acid residue represented by the general formula (5) can be synthesized by an esterification reaction of an acid anhydride group of a terracarboxylic dianhydride and a hydroxyl group of a diol compound.

The tetracarboxylic dianhydride is not particularly limited, but for example, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4. '-Oxydiphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanenianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and derivatives thereof, etc. However, the present invention is not limited to these. Further, one type may be used alone or two or more types may be used in combination.

The diol compound is not particularly limited, but for example, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, polyethylene. Examples thereof include glycol, polypropylene glycol, polytetramethylene glycol, hydride bisphenol A and the like. Further, examples of commercially available products include Kuraray Polyol C-1015N (manufactured by Kuraray Co., Ltd.)), Clarepolyol C-1065N (manufactured by Kuraray Co., Ltd.), and DURANOL-T5651 (manufactured by Asahi Kasei Chemicals Co., Ltd.). However, it is not limited to these. Further, one type may be used alone or two or more types may be used in combination.

The structure of the general formula (7) can be introduced by reacting the carboxyl group of the general formula (5) with a hydroxyl group-containing (meth) acrylate compound. The hydroxyl group-containing (meth) acrylate compound is not particularly limited, and for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth). Acrylate, 2-Hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, glycerol mono Examples thereof include (meth) acrylate, but the present invention is not limited thereto. Further, one type may be used alone or two or more types may be used in combination.

Polymaleic acid and its derivatives include polymaleic acid, isobutylene / maleic anhydride copolymer, styrene / maleic anhydride copolymer, methylvinyl ether / maleic anhydride copolymer, α-methylstyrene / maleic anhydride copolymer. , Rosin-modified maleic anhydride, and some or all of their carboxyl groups esterified, Marquid, Traffics, Alaster (trade name, manufactured by Arakawa Chemical Industry Co., Ltd.), X-288, Examples thereof include, but are not limited to, X-220, US-1243, X-200, and X-205 (above, trade name, manufactured by Seikou PMC Co., Ltd.). Further, these may be used alone or in combination of two or more.

The content of the polymer B is not particularly limited, but from the viewpoint of improving the film thickness unevenness of the cured film on and around the electrode, 5 parts by weight or more is preferable with respect to 100 parts by weight of the total of the polymer A and the polymer B. , 8 parts by weight or more is more preferable. On the other hand, from the viewpoint of controlling the solubility in an alkaline developer during photolithography processing, which will be described later, and maintaining high dielectric property derived from the inorganic particles contained in the polymer A, 60 parts by weight or less is preferable, and 30 parts by weight or less. Is more preferable, and 20 parts by weight or less is further preferable.

Within these ranges, it is possible to obtain the contrast between the exposed portion and the unexposed portion during photolithography while maintaining the high dielectric constant of the cured film. "The contrast between the exposed part and the unexposed part can be obtained" means, for example, in the case of a positive photosensitive material, there is no residual film in the exposed part, and the unexposed part is suppressed in solubility in a developing solution. It means that a cured film having a desired film thickness remains.

The content of the inorganic particles in the total of 100 parts by weight of the polymer A and the polymer B is not particularly limited, but from the viewpoint of increasing the dielectric constant of the cured film, 15 parts by weight or more is preferable, and 30 parts by weight is preferable. The above is particularly preferable. On the other hand, from the viewpoint of the dispersibility of the polymer A in the solution state, 80 parts by weight or less is preferable.

The inclusion of polymer A and polymer B in the resin composition is ^{an analytical method such as FT-IR, 1} H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, pyrolysis GC-MS, LC-MS, etc. Can be analyzed by combining.

(solvent)
The solvent used in the resin composition of the present invention is not particularly limited, and is, for example, ether, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy. -2-Pentanone, 4-Hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate (boiling point: 151 ° C), butyl lactate (boiling point: 186 ° C), propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propropylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol) Alcohols such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl Esters such as acetate and ethyl acetoacetate, ketones such as methylisobutylketone, diisopropylketone, diisobutylketone and acetylacetone, ethers such as diethyl ether, diisopropyl ether, din-butyl ether, diphenyl ether, diethylene glycol ethylmethyl ether and diethylene glycol dimethyl ether , Γ-Butylollactone, γ-Valerolactone, δ-Valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone and the like, but two or more of these may be contained. Among these, it is preferable to contain alcohols from the viewpoint of dispersibility of the inorganic particles.

(Photosensitive organic component)
As will be described later, when an element is formed using the resin composition of the present invention, it is preferable that the cured film is patterned by photolithography, and the resin composition of the present invention contains a photosensitive organic component. Is preferable. Photosensitive organic components include radically polymerizable compounds having an ethylenically unsaturated double-bonding group, photopolymerization initiators that cleave and / or react with UV light to generate radicals, chain transfer agents, and polymerization inhibitors. Examples thereof include an agent and a photoacid generator that generates an acid by light.

From the viewpoint of reducing the hysteresis of the FET element, a photoacid generator that does not generate radicals that cause charge traps in the gate insulating film is preferable. Low hysteresis can be achieved by reducing charge traps in the gate insulating film.

The photoacid generator is not particularly limited, and examples thereof include onium salt compounds, halogen-containing compounds, diazoketone compounds, diazomethane compounds, sulfon compounds, sulfonic acid ester compounds, and sulfonimide compounds. Specific examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like. Of these, the diazonaphthoquinone compound is preferable from the viewpoint of pattern processing accuracy and crack resistance of the obtained cured film. Preferred diazoketone compounds are esters of 1,2-naphthoquinone diazide-4-sulfonic acid and 2,2,3,4,4'-pentahydroxybenzophenone, 1,2-naphthoquinone diazide-4-sulfonic acid and 1,1, Esters with 1-tris (4-hydroxyphenyl) ethane and the like can be mentioned.

(Other ingredients)
The resin composition of the present invention may further contain inorganic particles to which the polymer is not bonded, in addition to the polymer to which the inorganic particles are bonded. The preferred material and shape of the inorganic particles to which the polymer is not bonded are the same as those of the above-mentioned inorganic particles to which the polymer is bonded.

Further, the resin composition in the present invention may contain a viscosity modifier, a surfactant, a stabilizer and the like, if necessary. Further, it may contain a residual solvent.

In particular, from the viewpoint of improving the coatability of the resin composition, it is preferable to include a surfactant. The type of surfactant is not particularly limited, and for example, "Megafuck (registered trademark)" F142D, F172, F173, F183, F445, F470, F475, F477 (above, Dainippon Ink and Chemicals). Fluorosurfactants such as Kogyo Co., Ltd., NBX-15, FTX-218, DFX-18 (manufactured by Neos Co., Ltd.), BYK-333, BYK-301, BYK-331, BYK-345, BYK A silicone-based surfactant such as −307 (manufactured by Big Chemie Japan Co., Ltd.), a polyalkylene oxide-based surfactant, a poly (meth) acrylate-based surfactant, or the like can be used. Two or more of these may be used. Of these, fluorine-based surfactants are particularly preferable.

<Element>
Examples of the device formed by using the resin composition of the present invention include a field effect transistor (FET) and a capacitor.

The FET is an element having a gate electrode, a gate insulating film, a source electrode, a drain electrode, and a semiconductor layer in contact with the source electrode and the drain electrode, and by applying and drying the resin composition of the present invention. A gate insulating film is obtained.

The capacitor is an element having a lower electrode, an upper electrode, and a dielectric film between the lower electrode and the upper electrode, and the dielectric film can be obtained by applying and drying the resin composition of the present invention.

Examples of the method for manufacturing such a device include the following examples.
(Manufacturing Example 1)
A method for manufacturing an element, which comprises the following (step 1) to (step 3).
(Step 1) Step of forming a conductive pattern to be a lower electrode on a substrate (Step 2) The resin composition according to any one of claims 1 to 7 is applied onto a substrate on which the conductive pattern is formed. And the process of drying and obtaining a coating film,
(Step 3) A step of forming a conductive pattern as an upper electrode on the coating film.
(Manufacturing Example 2)
A method for manufacturing an element, which comprises the following (step 1') to (step 3').
(Step 1') A step of forming a conductive pattern to be a lower electrode on a substrate (Step 2') The resin composition according to any one of claims 1 to 7 is applied onto a substrate on which the conductive pattern is formed. After coating and drying to obtain a coating film, the coating film is irradiated with active chemical rays via a photomask and developed to form a dielectric pattern having an opening on the conductive pattern. (Step 3') A step of forming a conductive pattern to be an upper electrode on the dielectric pattern.

Hereinafter, specific examples of the device obtained by using the resin composition of the present invention will be described in more detail with reference to the drawings. However, the elements obtained by using the resin composition of the present invention are not limited to the following.

[FET]
FIG. 1 is a schematic cross-sectional view showing an FET. In this structure, the insulating base material 100, the gate electrode 11, the gate insulating film 12, the source electrode 13, the drain electrode 15, and the semiconductor layer 14 in contact with the source electrode and the drain electrode are provided. The semiconductor layer and the gate electrode are electrically separated by a gate insulating film.

2 to 6 are schematic cross-sectional views showing a modified example of the FET. In the modified example 1 shown in FIG. 2, the gate electrode 11 and the source electrode 13 / drain electrode 15 do not overlap, and the width of the semiconductor layer 14 and the width of the gate electrode match. In the second modification shown in FIG. 3, there is an overlap between the gate electrode 11 and the source electrode 13 and the drain electrode 15. In the modified example 3 shown in FIG. 4, the gate electrode 11 and the source electrode 13 / drain electrode 15 do not overlap, and the width of the semiconductor layer 14 is larger than the width of the gate electrode. In the modified example 4 shown in FIG. 5, the gate electrode 11 and the source electrode 13 overlap each other.

1 to 5 are examples of a bottom gate structure, but the modified example 5 shown in FIG. 6 is an example of a top gate structure in which the gate electrode 11 and the drain electrode 15 overlap.

(Gate insulating film)
The gate insulating film preferably has a relative permittivity of 4 or more, more preferably 7 or more, further preferably 8.5 or more, and particularly preferably 10 or more. When the relative permittivity is in the above range, the on-current of the FET can be increased. The relative permittivity is preferably 20 or less, more preferably 15 or less, further preferably 13.5 or less, and particularly preferably 12 or less. When the relative permittivity is in the above range, excessive dielectric loss due to the gate insulating film can be prevented, and in particular, an FET driven by a radio wave in a high frequency band of 100 MHz or more can perform accurate operation. _{The relative permittivity ε r} of the gate insulating film can be calculated using the following equation (a).

ε _r = C ・ D / (S ・ ε ₀ ) (a)
However, C (F) is the capacitance of the gate insulating film, D (m) is the thickness of the gate insulating film, S (m ² ) is the area of the electrode sandwiching the gate insulating film, and ε ₀ is the permittivity of the vacuum (8). .85 × ^10-12 F / m).

The content of the inorganic particles in the gate insulating film is preferably 10 vol% or more, more preferably 15 vol% or more, and particularly preferably 20 vol% or more in terms of volume fraction. Similarly, the content is preferably 60 vol% or less, more preferably 50 vol% or less, and particularly preferably 40 vol% or less.

The thickness of the gate insulating film is preferably 10 nm or more, more preferably 25 nm or more, and particularly preferably 50 nm or more. The thickness of the gate insulating film is preferably 1000 nm or less, more preferably 750 nm or less, and particularly preferably 500 nm or less. The gate insulating film is composed of a single layer or a plurality of layers. In the case of a plurality of layers, a plurality of the above-mentioned preferable gate insulating films may be laminated, or the preferred gate insulating film and a known gate insulating film may be laminated.

Further, an orientation layer can be provided between the gate insulating film and the semiconductor layer described later. As the material of the orientation layer, known materials such as a silane compound, a titanium compound, an organic acid, and a heteroorganic acid can be used, and an organic silane compound is particularly preferable.

(Second insulating film)
The FET of the present invention may have a second insulating film on the side opposite to the gate insulating film with respect to the semiconductor layer described later. Here, the side opposite to the gate insulating film with respect to the semiconductor layer refers to, for example, the lower side of the semiconductor layer when the gate insulating film is provided on the upper side of the semiconductor layer. As a result, the threshold voltage and hysteresis can be reduced, and a high-performance FET can be obtained. Examples of the second insulating layer and a method for producing the second insulating layer preferably used include known ones such as those described in International Publication No. 2019/065561.

(Semiconductor layer)
The semiconductor layer in the present invention is not particularly limited as long as it has semiconductor properties, such as inorganic semiconductors such as silicon semiconductors and oxide semiconductors, organic semiconductors such as pentacene and polythiophene derivatives, and carbon such as carbon nanotubes (CNT) and graphene. Semiconductors can be used. Among these, CNTs are excellent in that they have high carrier mobility and can be applied with a simple coating process at low cost.

The CNTs are a single-walled CNT in which one carbon film (graphene sheet) is wound in a cylindrical shape, a two-walled CNT in which two graphene sheets are wound concentrically, and a plurality of graphene sheets are concentric. Any of the multi-walled CNTs wound around the CNTs may be used, and two or more of these may be used. It is preferable to use single-walled CNTs from the viewpoint of exhibiting the characteristics of semiconductors. It is more preferable that the single-walled CNT contains 90% by mass or more of the semiconductor type single-walled CNT. More preferably, the single-walled CNT contains 95% by mass or more of the semiconductor-type single-walled CNT.

The content ratio of the semiconductor type single-walled CNT can be calculated from the absorption area ratio of the visible-near infrared absorption spectrum. CNTs can be obtained by methods such as an arc discharge method, a chemical vapor deposition method (CVD method), and a laser ablation method.

Further, the CNT complex in which the conjugated polymer is attached to at least a part of the CNT surface is particularly preferable because it has excellent dispersion stability in a solution and low hysteresis can be obtained. The state in which the conjugated polymer is attached to at least a part of the surface of the CNT means a state in which a part or the whole of the surface of the CNT is covered with the conjugated polymer. It is presumed that the conjugated polymer can coat the CNTs because the interaction occurs due to the overlap of the π-electron clouds derived from the respective conjugated structures. Whether or not the CNTs are coated with the conjugated polymer can be determined by approaching the color of the conjugated polymer from the color of the uncoated CNTs as the reflected color of the coated CNTs. Quantitatively, the presence of deposits and the mass ratio of deposits to CNT can be identified by elemental analysis, X-ray photoelectron spectroscopy, or the like. Further, the conjugated polymer attached to the CNT can be used regardless of the molecular weight, the molecular weight distribution and the structure.

The methods for adhering the conjugated polymer to CNT are (I) a method of adding CNT to the molten conjugated polymer and mixing it, and (II) dissolving the conjugated polymer in a solvent and CNT in this. (III) A method of adding a conjugated polymer to a place where CNTs have been pre-dispersed in advance by ultrasonic waves or the like in a solvent and mixing, (IV) A method of adding and mixing a conjugated polymer in a solvent. And CNT are put in, and this mixing system is irradiated with ultrasonic waves to mix. A plurality of methods may be combined.

The length of the CNT is preferably shorter than the distance (channel length) between the source electrode and the drain electrode. The average length of CNT depends on the channel length, but is preferably 2 μm or less, more preferably 0.5 μm or less. Generally, commercially available CNTs have a distribution in length and may contain CNTs longer than the channel length. Therefore, it is preferable to add a step of making the CNTs shorter than the channel length. For example, a method of cutting into short fibers by acid treatment with nitric acid, sulfuric acid or the like, ultrasonic treatment, or freeze pulverization method is effective. Further, it is more preferable to use the separation by a filter together in terms of improving the purity.

The diameter of the CNT is not particularly limited, but is preferably 1 nm or more and 100 nm or less, and more preferably 50 nm or less.

It is preferable to provide a step of uniformly dispersing CNTs in a solvent and filtering the dispersion liquid with a filter. By obtaining CNTs smaller than the filter pore size from the filtrate, CNTs shorter than the channel length can be efficiently obtained. In this case, a membrane filter is preferably used as the filter. The pore size of the filter used for filtration may be smaller than the channel length, preferably 0.5 to 10 μm.

Examples of the conjugated polymer that coats the above CNT include a polythiophene polymer, a polypyrrole polymer, a polyaniline polymer, a polyacetylene polymer, a poly-p-phenylene polymer, and a poly-p-phenylene vinylene-based weight. Examples thereof include a thiophene-heteroarylene polymer having a thiophene unit and a heteroaryl unit in a repeating unit, and two or more of these may be used. As the above polymer, one in which a single monomer unit is lined up, one in which different monomer units are block copolymerized, one in which random copolymerization is performed, one in which graft polymerization is used, or the like can be used.

Further, the semiconductor layer may be a mixture of a CNT complex and an organic semiconductor. By uniformly dispersing the CNT complex in the organic semiconductor, it is possible to realize low hysteresis while maintaining the characteristics of the organic semiconductor itself. Examples of the organic semiconductor preferably used include known ones such as those described in International Publication No. 2019/065561.

The content of the CNT composite in the semiconductor layer containing the CNT composite and the organic semiconductor is preferably 0.01 part by mass or more and 3 parts by mass or less, and more preferably 1 part by mass or less with respect to 100 parts by mass of the organic semiconductor.

The semiconductor layer may contain other carbon materials. Examples of other carbon materials used here include graphene and fullerenes.

The semiconductor layer may further contain an insulating material. Examples of the insulating material used here include, but are not limited to, polymer materials such as poly (methyl methacrylate), polycarbonate, and polyethylene terephthalate.

The semiconductor layer may be a single layer or a plurality of layers. The film thickness of the semiconductor layer is preferably 1 nm or more and 200 nm or less, and more preferably 100 nm or less. By setting the film thickness in this range, it becomes easy to form a uniform thin film, and the variation in FET characteristics can be reduced. The film thickness can be measured by an atomic force microscope, an ellipsometry method, or the like.

(substrate)
The material used for the substrate may be any material as long as at least the surface on which the electrodes (gate electrodes or source / drain electrodes) are arranged is insulating. For example, inorganic materials such as silicon wafers, glass, sapphire, alumina sintered body; polyimide, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polyvinylidene fluoride, polysiloxane, polyvinylphenol (PVP), polyester, polycarbonate, etc. Organic materials such as polysulfone, polyethersulfone, polyethylene, polyphenylene sulfide, and polyparaxylene are preferably used.

Further, for example, a plurality of materials such as a PVP film formed on a silicon wafer and an acrylic resin, a polyester resin, and a polysiloxane formed on a polyethylene terephthalate as an adhesion improver for a lower electrode are laminated. You may.

Among these, polyethylene terephthalate (PET) is preferable as the substrate material from the viewpoint of device flexibility and manufacturing cost, and particularly from the viewpoint of substrate surface smoothness, a PET film to which fillers such as silica particles are not added is used. A film having a coat layer containing silica nanoparticles formed on its surface is preferable.

In a normal PET film, since silica particles are contained in the film, the surface smoothness of the substrate is low, and when an element is manufactured from this film, the gate insulating film tends to leak at the convex portion. On the other hand, a film in which a coat layer containing silica nanoparticles is formed on the surface of a PET film to which a filler such as silica particles is not added has high surface smoothness. Therefore, in the element made of this film, leakage in the gate insulating film is unlikely to occur.

(electrode)
Materials used for gate electrodes, source electrodes and drain electrodes include, for example, conductive metal oxides such as tin oxide, indium oxide, indium tin oxide (ITO); platinum, gold, silver, copper, iron, tin, zinc, Metals such as aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, magnesium, palladium, molybdenum, amorphous silicon and polysilicon and their alloys; inorganic conductive substances such as copper iodide and copper sulfide; polythiophene, Polypyrrole, polyaniline; a complex of polyethylenedioxythiophene and polystyrene sulfonic acid; a conductive polymer whose conductivity has been improved by doping with iodine or the like; a conductor such as a carbon material can be mentioned. These materials may be used alone, or a plurality of materials may be laminated or mixed.

It is preferable to use metal particles as the conductor. The use of metal particles has the effect of improving the bending resistance of the device. It is considered that the reason for this is that unevenness is formed on the surface of the conductive film, and the anchor effect generated by the gate insulating film entering the unevenness improves the adhesion between the conductive film and the gate insulating film.

Specifically, as the metal particles, metal particles containing at least one of gold, silver, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, ruthenium oxide, chromium, titanium, carbon and indium are preferable. .. These metal particles can be used alone, as alloys, or as mixed particles. Among these, gold, silver, copper or platinum particles are preferable from the viewpoint of conductivity. Above all, silver particles are more preferable from the viewpoint of cost and stability. Further, from the viewpoint of reducing the electrical resistivity of the conductive film, it is more preferable to contain carbon black.

It is preferable that at least one of the gate electrode and the source electrode / drain electrode contains an organic component. The inclusion of an organic component improves the adhesion between the electrode and the gate insulating film. Further, since the organic component contains the photosensitive organic component, the electrode pattern can be processed by photolithography without using a resist, and the productivity can be further improved. From the viewpoint of further enhancing these effects, it is preferable that both the gate electrode and the source electrode / drain electrode contain an organic component.

The organic component is not particularly limited, and examples thereof include a monomer, an oligomer, and a polymer. The oligomer or polymer is not particularly limited, and acrylic resin, epoxy resin, novolak resin, phenol resin, polyimide precursor, polyimide and the like can be used, but acrylic resin is preferable from the viewpoint of crack resistance during bending. It is presumed that this is because the glass transition temperature of the acrylic resin is 100 ° C. or lower, and the conductive film softens during thermosetting, and the binding between the conductor particles is strengthened.

Further, the photosensitive organic component contains a monomer, an oligomer, a polymer and / or an addition reaction thereof having a polymerizable unsaturated group in the molecule.

As the monomer having a polymerizable unsaturated group in the molecule, a compound having an active carbon-carbon unsaturated double bond can be used. As the functional group, monofunctional compounds and polyfunctional compounds having a group selected from a vinyl group, an allyl group, an acrylate group, a methacrylate group and an acrylamide group can be applied. One or two or more of these can be used.

The monomer is preferably contained in the range of 1% by mass to 15% by mass, more preferably in the range of 2% by mass to 10% by mass, based on the total mass part of the electrode material. An oligomer or polymer having a polymerizable unsaturated group in the molecule can be obtained by adding a polymerizable unsaturated group to the side chain or the end of the molecule with respect to the oligomer or polymer.

Preferred polymerizable unsaturated groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group and a methacrylic group.

Examples of the method for adding such a side chain to the oligomer or polymer include known methods such as the method described in International Publication No. 2019/065561.

Since the electrode material is photocurable, it preferably contains a photopolymerization initiator. The photopolymerization initiator is selected depending on the light source used for photocuring, and a photoradical polymerization initiator, a photocationic polymerization initiator, or the like can be used.

The photopolymerization initiator is preferably contained in the range of 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 10% by mass, based on the total mass part of the electrode material. If the amount of the photopolymerization initiator is too small, the photocuring may be insufficient, and if the amount of the photopolymerization initiator is too large, the compatibility may be poor.

By using a sensitizer together with a photopolymerization initiator, the sensitivity can be improved and the effective wavelength range for the reaction can be expanded. When the electrode material contains a sensitizer, the content thereof is preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 10% by mass, based on the photosensitive organic component. If the amount of the sensitizer is too small, the effect of improving photocuring is not exhibited, and if the amount of the sensitizer is too large, the compatibility may be poor.

The amount of the conductor in the conductive film is preferably in the range of 70 to 95 wt% of the conductive film, more preferably 80 wt% or more as the lower limit and 90 wt% or less as the upper limit, respectively. Within this range, the specific resistance value of the conductive film and the probability of disconnection can be reduced.

As a method for forming the electrode, a method using known techniques such as resistance heating vapor deposition, electron beam, sputtering, plating, CVD, ion plating coating, inkjet, printing, or a paste containing the organic component and a conductor is spun. It is applied on an insulating substrate by known techniques such as coating method, blade coating method, slit die coating method, screen printing method, bar coater method, mold method, printing transfer method, immersion pulling method, etc. Examples thereof include a method of forming by drying using. There is no particular limitation as long as it can be conducted.

When the electrode is formed by applying a paste, an organic solvent may be contained for forming the paste. By using an organic solvent, the viscosity of the paste can be adjusted and the surface smoothness of the coating film can be improved.

The width, thickness, and spacing of the electrodes are arbitrary. The electrode width is preferably 5 μm to 1 mm, the thickness is 0.01 μm to 100 μm, and the electrode spacing is preferably 1 μm to 500 μm, but is not limited thereto.

As a method for forming the electrode into a pattern, the electrode thin film produced by the above method may be patterned into a desired shape by a known photolithography method, or the electrode, wiring and connection material may be vapor-deposited or sputtering. Occasionally, the pattern may be formed through a mask having a desired shape. Further, the pattern may be directly formed by using an inkjet or a printing method.

The electrode patterns may be formed by processing them separately, or at least two of them may be processed together to form the electrode patterns. From the viewpoint of reducing the processing process and connecting the patterns, it is preferable to process the electrode patterns collectively.

(Method of manufacturing FET)
The method of manufacturing the FET shown in the configuration of FIG. 1 will be described below. The manufacturing method is not limited to the following.

(Step 1) Step of Forming a Conductive Pattern to be a Lower Electrode on a Substrate First, a conductive pattern to be a gate electrode 11 is formed on a substrate 100. Examples of the forming method include known methods such as metal vapor deposition, spin coating method, blade coating method, slit die coating method, screen printing method, bar coating method, mold method, print transfer method, immersion pulling method, and inkjet method. In forming the conductive pattern, the pattern may be directly formed using a mask or the like, or a resist is applied onto the formed gate electrode, the resist film is exposed and developed into a desired pattern, and then etching is performed. It is also possible to pattern the gate electrode by doing so. Further, when a conductive paste having a photosensitive organic component is used, the gate electrode can be patterned by photolithography without using a resist.

(Step 2) A step of applying and drying the resin composition of the present invention on a substrate on which the conductive pattern is formed to obtain a coating film. Next, a gate insulating film 12 is formed on the substrate on which the conductive pattern is formed. To form. As a method for forming the gate insulating film 12, the resin composition of the present invention is applied onto a substrate, dried to obtain a coating film, and then the coating film is heated and cured to cure the gate insulating film 12. Can be formed.

Known methods for applying the resin composition of the present invention include a spin coating method, a blade coating method, a slit die coating method, a screen printing method, a bar coating method, a mold method, a printing transfer method, a dipping pulling method, and an inkjet method. An application method can be mentioned.

The drying temperature for obtaining the coating film is preferably 50 to 150 ° C., more preferably 60 to 140 ° C., further preferably 70 ° C. to 130 ° C., and particularly preferably 80 ° C. to 120 ° C. When the drying temperature is in this range, it is preferable from the viewpoint that it becomes easier to remove the solvent from the coating film and to process it into a desired shape at the time of patterning described later. The drying time is preferably 0.5 to 5 minutes, more preferably 1 to 3 minutes. When the drying time is within this range, it is preferable from the viewpoint that it becomes easier to remove the solvent from the coating film and to process it into a desired shape at the time of patterning described later.

Further, the temperature of the heat treatment of the coating film for curing the coating film to obtain the gate insulating film is preferably in the range of 100 to 300 ° C, more preferably 120 to 250 ° C. When the heat treatment temperature is in this range, a sufficiently cured gate insulating film can be obtained.

Further, when the FET is formed on the plastic substrate, 120 to 200 ° C. is preferable, and 120 to 150 ° C. is particularly preferable. When the temperature is in this range, the shrinkage of the plastic substrate during the heat treatment can be suppressed.

The heat treatment time of the coating film is preferably 0.5 to 60 minutes, more preferably 5 to 30 minutes. When the heat treatment time is within this range, a sufficiently cured gate insulating film can be obtained.

(Step 3) Step of Forming a Conductive Pattern to be an Upper Electrode on the Coating Film Next, a conductive pattern to be a source electrode 13 and a drain electrode 15 is formed on the gate insulating film. Similar to the gate electrode 11, the method of forming the source electrode 13 and the drain electrode 15 includes, for example, metal deposition, spin coating method, blade coating method, slit die coating method, screen printing method, bar coating method, mold method, and printing transfer method. , Known methods such as a dipping pulling method and an inkjet method can be mentioned. In forming the conductive pattern, the pattern may be directly formed using a mask or the like, or a resist is applied onto the formed electrodes, and the resist film is exposed and developed into a desired pattern and then etched. This makes it possible to pattern the source electrode and the drain electrode. Further, when a conductive paste having a photosensitive organic component is used, it is also possible to pattern the gate electrode by photolithography from only the conductive paste without using a resist.

The above (step 1) to (step 3) can be replaced with (step 1') to (step 3').

In (Step 2'), the coating film can be patterned after performing the same operation as in (Step 2) until the coating film is obtained. When forming a circuit in which FETs are combined, it may be necessary to form a pattern having an opening (contact hole) on the conductive pattern in order to take conduction from the conductive pattern existing in the lower part of the insulating layer. ..

A method for forming a pattern of a coating film using a composition containing a photosensitive organic component will be described. Chemical rays are irradiated (exposed) from above the coating film through a mask having a desired pattern. Examples of chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. Next, the exposed coating film is developed. Examples of the developing solution include known ones such as tetramethylammonium hydroxide and those described in International Publication No. 2019/065561.

It is also possible to pattern the gate insulating film by applying a resist on the gate insulating film, exposing and developing the resist film in a desired pattern, and then treating the resist film with an etching solution such as hydrofluoric acid. With this method, patterning is possible even when the gate insulating film is made of a composition containing no photosensitive organic component. However, since the number of steps increases, it is preferable to pattern the gate insulating film using an insulating layer material having a photosensitive organic component from the viewpoint of excellent productivity. Furthermore, from the viewpoint of improving the crack resistance of the obtained gate insulating film,
After (step 3) or (step 3'), the FET is obtained by forming the semiconductor layer 14 on the gate insulating film on which the source electrode and the drain electrode are formed. As a method for forming the semiconductor layer 14, a dry method such as resistance heating vapor deposition, electron beam, sputtering, or CVD can be used, but it is preferable to use a coating method from the viewpoint of manufacturing cost and compatibility with a large area. .. Examples of the coating method include known coating methods such as spin coating method, blade coating method, slit die coating method, screen printing method, bar coating method, mold method, printing transfer method, immersion pulling method, and inkjet method. The coating method can be selected according to the coating film characteristics to be obtained, such as coating film thickness control and orientation control. Using these methods, the semiconductor layer is formed so that the semiconductor layer and the conductive patterns serving as the source electrode 13 and the drain electrode 15 are in contact with each other. After forming the semiconductor layer, the source electrode and the drain electrode may be formed.

In particular, when forming a semiconductor layer containing CNT, it is preferable to apply a solution containing CNT on the gate insulating film. In this case, the coating method is not particularly limited, but the use of the inkjet method is excellent in that the amount of the solution used can be reduced and the productivity can be increased. The solution containing CNTs can be prepared by stirring CNTs in a solvent by a stirring treatment using a known dispersion device such as an ultrasonic homogenizer.

When the semiconductor layer is formed by coating, the formed coating film is dried under the atmosphere, under reduced pressure, or under the atmosphere of an inert gas (nitrogen or argon). The drying temperature is preferably 50 to 150 ° C.

A step of forming an oriented layer between the gate insulating film 12 and the semiconductor layer 14 by the same method as the method of forming the coating film of the gate insulating film material may be added. Further, a step of forming the second insulating layer on the side opposite to the gate insulating film 12 with respect to the semiconductor layer 14 in the same manner as the semiconductor layer 14 may be added.

[Capacitor]
FIG. 7 is a schematic cross-sectional view showing a capacitor. In this structure, the insulating base material 200 has a pair of conductive films, a lower electrode 21, a dielectric film 22, and an upper electrode 23. The lower electrode 21 and the upper electrode 23 are not electrically connected, and a dielectric film 22 is formed between the lower electrode 21 and the upper electrode 23. The dielectric film 22 is obtained by applying, drying and curing with the resin composition of the present invention.

8 to 10 are schematic cross-sectional views showing a modified example of the above capacitor. In the first modification shown in FIG. 8, the dielectric film 22 is formed so as to cover the lower electrode 21 on the insulating base material 200, and the upper electrode 23 is further formed so as to cover the dielectric film 22. In the second modification shown in FIG. 9, the lower electrode 21 and the upper electrode 23 are present on the insulating base material 200, and the dielectric film 22 is formed between them. In the modified example 3 shown in FIG. 10, the dielectric film 22 exists so as to cover a part of the upper electrode 21 on the insulating base material 200, and the upper electrode 23 is further formed so as to cover a part of the dielectric film 22. There is.

Regarding the materials and manufacturing methods of the insulating base material, the dielectric film, the upper electrode and the lower electrode, the same matters as those in the insulating base material, the gate insulating film and the gate electrode in the above-mentioned FET apply.

<Circuit>
A circuit can be configured by combining the above FET and a capacitor. The circuit is not particularly limited, and examples thereof include a rectifier circuit, a modulation circuit, a memory circuit, a power supply circuit, a reference voltage / current circuit, a data converter circuit, an operational amplifier, and the like, but the circuit is not limited thereto. Further, these may be used alone or in combination of two or more.

FIG. 11 is an example of a rectifier circuit including the FET 301 and the capacitor element 302. In the structure of FIG. 11, a capacitor 302 composed of a lower electrode 32, an upper electrode 37, and an insulating film (dielectric film) 33, a gate electrode 31, an insulating film 33 (gate insulating film), and a source electrode are placed on the insulating base material 300. An FET 301 composed of 35, a drain electrode 36 and a semiconductor layer 34, a wiring 38, and a via 39 are provided. In FIG. 11, the dielectric film of the capacitor 302 and the gate insulating film of the FET 301 are shared, and the same material is used. FIG. 11 illustrates a structure in which the drain electrode 36 and the upper electrode 37 are electrically connected via the wiring 38, but the drain electrode 36 and the lower electrode 32 are electrically connected via the wiring 38 and the via 39. It may be connected to. Further, although the FET having a bottom gate structure is shown in FIG. 11, an FET having a top gate structure may be used. Further, although FIG. 11 shows a circuit in which the dielectric film of the capacitor 302 and the gate insulating film of the FET 301 are common, as shown in FIGS. 12 and 13, insulating films 33A and 33B made of different materials may be used. ..

As the insulating base material, the dielectric film, the gate electrode, the upper electrode, and the lower electrode, the same materials and manufacturing methods as those used in the first and second embodiments can be used. Further, for vias and wiring, the same materials and manufacturing methods as those for the lower electrode and the upper electrode can be used.

(Applicability of element)
The element manufactured by using the resin composition of the present invention can be applied to ICs of various electronic devices, wireless communication devices such as RFID tags, TFT arrays for displays, sensors, open detection systems and the like.

<Wireless communication device>
The circuit manufactured by using the resin composition of the present invention can be applied to a wireless communication device. This wireless communication device transmits from an antenna mounted on a reader / writer, such as an RFID (Radio Frequency Identification) tag, which is a non-contact tag such as a product tag, an anti-cash tag, various tickets, and a smart card. It is a device that performs telecommunications by receiving a carrier wave. Specifically, for example, the antenna of the RFID tag receives the radio signal transmitted from the antenna mounted on the reader / writer, converts it into a direct current by the rectifier circuit, and causes the RFID tag to generate electricity. Next, the generated RFID tag receives a command from the radio signal and performs an operation in response to the command. After that, the answer of the result according to the command is transmitted as a radio signal from the antenna of the RFID tag to the antenna of the reader / writer. The operation according to the command is executed by a demodulation circuit, a control circuit, a modulation circuit, or the like.

The wireless communication device of the present invention has at least the above-mentioned FET and an antenna. As a more specific configuration, for example, as shown in FIG. 14, the power generation unit 45 that rectifies the modulated wave signal from the outside received by the antenna 40 and supplies power to each unit, and demodulates the modulated wave signal. The demodulation circuit 41 that sends the data to the control circuit, the modulation circuit 43 that modulates the data sent from the control circuit and sends it to the antenna, writes the data demodulated by the demodulation circuit 41 to the storage circuit 44, and reads the data from the storage circuit 44. A wireless communication device composed of a control circuit 42 for transmitting to the modulation circuit 43 and electrically connected to each circuit unit can be mentioned. At least one or more of the power generation unit, the demodulation circuit, the control circuit, the modulation circuit, and the storage circuit includes the above-mentioned elements, and may further include a capacitor, a resistance element, a diode, and the like. The storage circuit is further composed of a non-volatile storage unit such as a read-only storage unit in which information is written at the time of manufacture, an EEPROM (Electrically Erasable Programmable Read-Only Memory), and a FeRAM (Ferroelectric Random Access Memory). You may have. The power generation unit is composed of a capacitor and a diode.

The antenna, capacitor, resistance element, diode, and non-volatile rewritable storage unit may be any commonly used material, and the material and shape used are not particularly limited. Further, the material for electrically connecting each of them may be any conductive material that can be generally used. The connection method may be any method as long as it can be electrically conductive, and the width and thickness of the connection portion are arbitrary.

<Product tag>
A product tag using the above wireless communication device will be described. This product tag has, for example, a substrate and the wireless communication device coated with the substrate.

The substrate is formed of, for example, a non-metallic material such as paper formed in a flat plate shape. For example, the substrate has a structure in which two sheets of flat paper are bonded together, and the wireless communication device is arranged between the two sheets of paper. In the storage circuit of the wireless storage device, for example, individual identification information for identifying an individual product is stored in advance.

Wireless communication is performed between this product tag and the reader / writer. A reader / writer is a device that wirelessly reads and writes data to a product tag, and exchanges data with the product tag during the distribution process of the product or at the time of payment. Known readers / writers can be used, for example, portable ones and fixed type readers / writers installed at cash registers.

Specifically, the product tag has an identification information reply function that wirelessly returns the stored individual identification information in response to a command from a predetermined reader / writer requesting transmission of the individual identification information. As a result, for example, at a product checkout register, a large number of products can be identified at the same time without contact, and payment processing can be facilitated and speeded up as compared with identification by a barcode.

For example, when accounting for a product, if the reader / writer sends the product information read from the product tag to the POS (Point of sale system) terminal, the product specified by the product information on the POS terminal. It is possible to register for sale.

Hereinafter, the present invention will be described in more detail based on examples. The present invention is not limited to the following examples.

(1) Measuring the film thickness of the insulating layer Using an optical interference type spectroscopic film thickness measuring machine (OPTM-A2 manufactured by Otsuka Electronics Co., Ltd.), the film thickness of the insulating layer on the lower electrode and the insulating base material around the lower electrode The film thickness of the upper insulating layer was measured.
The film thickness was measured at 5 points on the lower electrode and around the lower electrode, and the difference between the maximum value and the minimum value was defined as the film thickness unevenness, and the evaluation was performed according to the following criteria.
A + (remarkably good): Film thickness unevenness is less than ± 15 nm.
A (very good): Film thickness unevenness is less than ± 25 nm.
B (good): Film thickness unevenness is ± 25 nm or more and less than ± 50 nm.
C (possible): Film thickness unevenness is ± 50 nm or more and less than ± 100 nm.
D (impossible): Film thickness unevenness is ± 100 nm or more.

(2) Measurement of Relative Pertivity of Insulation Layer The insulator solution shown in Table 1 is spin-coated on an aluminum substrate (800 rpm x 10 seconds), heat-treated at 110 ° C for 2 minutes, and then 150 ° C 30 using a drying oven. A cured film having a film thickness of 400 nm was formed by heat treatment for a minute. Next, a circular aluminum electrode having a diameter of 5 mm was deposited and formed on the cured film. The capacitance of this film was measured at 25 ° C. and 1 MHz using a precision impedance analyzer (manufactured by Agilent, type 4294A). Based on the above conditions and measured values, the relative permittivity ε _r of the cured film was determined according to equation (a).

(3) Preparation of Capacitor The capacitor shown in FIG. 15 was manufactured. Copper is vacuum-deposited on a PET film (trade name "U48", manufactured by Toray Industries, Inc.) 500 having a film thickness of 50 μm so as to have a film thickness of 100 nm by a resistance heating method, and a photoresist (trade name "trade name") is deposited on the copper film. "LC140-10cP", manufactured by Rohm & Haas Co., Ltd., was spin-coated (1000 rpm x 20 seconds) and dried by heating at 100 ° C. for 10 minutes. The prepared photoresist film was pattern-exposed through a mask using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.), and then using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). It was shower-developed for 60 seconds with ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a 2.38 mass% TMAH aqueous solution, and then washed with water for 30 seconds. Then, it was etched with Cu-03 (trade name, manufactured by Kanto Chemical Co., Inc.) for 2 minutes, and then washed with water for 30 seconds. The lower electrode 51 was formed by immersing in JELK-101 (trade name, manufactured by Kanto Chemical Co., Inc.) for 2 minutes to peel off the resist, washing with water for 30 seconds, and then heating and drying at 120 ° C. for 20 minutes. Next, the resin composition of the present invention is spin-coated (800 rpm × 10 seconds) on a PET film on which the lower electrode 51 is formed, heat-treated at 110 ° C. for 2 minutes, and then heat-treated at 150 ° C. for 30 minutes using a drying oven. By doing so, a dielectric film 52 having a film thickness of 400 nm was formed. Next, the conductive paste of Preparation Example 2 was applied with a bar coater, and prebaked at 100 ° C. for 10 minutes in a drying oven. Then, after exposure using the exposure apparatus "PEM-8M", _{immersion development is performed in a 0.5% Na 2} CO ₃ solution for 30 seconds, rinsing with ultrapure water, and curing is performed at 140 ° C. for 30 minutes in a drying oven. , The upper electrode 53 was formed.

(4) Manufacture of FET The FET shown in FIG. 16 was manufactured. Copper is vacuum-deposited on a PET film (trade name "U48", manufactured by Toray Industries, Inc.) 600 with a film thickness of 50 μm so as to have a film thickness of 100 nm by a resistance heating method, and a photoresist (trade name "trade name") is deposited on the copper film. "LC140-10cP", manufactured by Rohm & Haas Co., Ltd., was spin-coated (1000 rpm x 20 seconds) and dried by heating at 100 ° C. for 10 minutes. The prepared photoresist film was pattern-exposed through a mask using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.), and then using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). It was shower-developed for 60 seconds with ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a 2.38 mass% TMAH aqueous solution, and then washed with water for 30 seconds. Then, it was etched with Cu-03 (trade name, manufactured by Kanto Chemical Co., Inc.) for 2 minutes, and then washed with water for 30 seconds. The gate electrode 61 was formed by immersing in JELK-101 (trade name, manufactured by Kanto Chemical Co., Inc.) for 2 minutes to peel off the resist, washing with water for 30 seconds, and then heating and drying at 120 ° C. for 20 minutes. Next, the resin composition of the present invention is spin-coated (800 rpm × 10 seconds) on a PET film on which the gate electrode 61 is formed, heat-treated at 110 ° C. for 2 minutes, and then heat-treated at 150 ° C. for 30 minutes using a drying oven. By doing so, a gate insulating film 62 having a film thickness of 400 nm was formed. Next, the semiconductor solution of Preparation Example 1 was inkjet-coated on the gate insulating film 62 and heat-treated at 150 ° C. for 30 minutes in the atmosphere to form the semiconductor layer 63. Next, the conductive paste of Preparation Example 2 was applied with a bar coater, and prebaked at 100 ° C. for 10 minutes in a drying oven. Then, after exposure using the exposure apparatus "PEM-8M", the mixture is _{immersed and developed in a 0.5% Na 2} CO ₃ solution for 30 seconds, rinsed with ultrapure water, and then cured in a drying oven at 140 ° C. for 30 minutes. , Source electrode 64 and drain electrode 65 were formed.

(5) Preparation of Rectifier Circuit A rectifier circuit including the FET 701 and the capacitor 702 shown in FIG. 17 was manufactured. Copper is vacuum-deposited on a PET film (trade name "U48", manufactured by Toray Industries, Inc.) 700 with a film thickness of 50 μm so as to have a film thickness of 100 nm by a resistance heating method, and a photoresist (trade name "trade name") is deposited on the copper film. "LC140-10cP", manufactured by Rohm & Haas Co., Ltd., was spin-coated (1000 rpm x 20 seconds) and dried by heating at 100 ° C. for 10 minutes. The prepared photoresist film was pattern-exposed through a mask using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.), and then using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). It was shower-developed for 60 seconds with ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a 2.38 mass% TMAH aqueous solution, and then washed with water for 30 seconds. Then, it was etched with Cu-03 (trade name, manufactured by Kanto Chemical Co., Inc.) for 2 minutes, and then washed with water for 30 seconds. Immerse in JELK-101 (trade name, manufactured by Kanto Chemical Co., Ltd.) for 2 minutes to peel off the resist, wash with water for 30 seconds, and heat and dry at 120 ° C. for 20 minutes to obtain the gate electrode 71 and capacitor of the FET element. The lower electrode 72 of the element was formed. Next, the resin composition of the present invention was spin-coated (800 rpm × 10 seconds) on a PET film on which the gate electrode 71 and the lower electrode 72 were formed, and heat-treated at 110 ° C. for 2 minutes. Then, after exposure using the exposure apparatus "PEM-8M", the film was immersed and developed in TMAH solution for 30 seconds, rinsed with ultrapure water, and a punched pattern was formed at a portion where the via 79 was formed. Then, by heat-treating at 150 ° C. for 30 minutes using a drying oven, an insulating film 73 having a thickness of 400 nm, which also serves as a gate insulating film of the FET element and a dielectric film of the capacitor element, was formed. Next, the semiconductor solution of Preparation Example 1 was inkjet-coated on the insulating film 73 and heat-treated at 150 ° C. for 30 minutes in the atmosphere to form the semiconductor layer 74. Next, the conductive paste of Preparation Example 2 was applied with a bar coater, and prebaked at 100 ° C. for 10 minutes in a drying oven. Then, after exposure using the exposure apparatus "PEM-8M", the film is _{immersed and developed in a 0.5% Na 2} CO ₃ solution for 30 seconds, rinsed with ultrapure water, and then cured at 140 ° C. for 30 minutes in a drying oven. , The source electrode 75 and drain electrode 76 of the FET element, the upper electrode 77 of the capacitor element, the wiring 78, and the via 79 were formed.

(6) Evaluation of Short Circuit Rate of Capacitors The inter-electrode current (Ie) when the applied voltage (Ve) was changed was measured for 100 manufactured capacitors. The semiconductor characteristic evaluation system 4200-SCS type (manufactured by Keithley Instruments Co., Ltd.) was used for the measurement, and the measurement was performed in the atmosphere (temperature 20 ° C., humidity 35%). An element having an electrode area of 1 mm ² was evaluated according to the following criteria, with an element having ^{an IE of 10-8} A or more at Ve = 10 V as a short-circuit element.
A (very good): The number of elements in which a short circuit was observed is 1 in 100 or less.
B (good): The number of elements in which a short circuit was observed is 2 or more and less than 5 out of 100.
C (possible): The number of elements in which a short circuit was observed is 5 or more and less than 10 out of 100.
D (impossible): The number of elements with short circuits is 10 or more out of 100.

(7) Evaluation of FET Leakage Rate The source-drain current (Id) -source-drain voltage (Vsd) characteristics when the gate voltage (Vg) was changed were measured for the 100 FETs produced. The semiconductor characteristic evaluation system 4200-SCS type (manufactured by Keithley Instruments Co., Ltd.) was used for the measurement, and the measurement was performed in the atmosphere (temperature 20 ° C., humidity 35%). The on-current was determined from the drain current value at Vg = −20 V. Further, an element having a gate-source current (Vgs) of ^10-8 A or more at Vg = 20 V was used as a leak element, and evaluation was performed according to the following criteria.
A (very good): The number of elements with leaks was 1 in 100 or less.
B (good): The number of elements with leaks is 2 or more and less than 5 out of 100.
C (possible): The number of elements with leaks is 5 or more and less than 10 out of 100.
D (impossible): The number of elements with leaks is 10 or more out of 100.

(8) Evaluation of rectifier circuit yield In the 100 rectifier circuits manufactured, when an AC current is input to the source electrode 74, the DC current output to the drain electrode 75 is measured, and the rectifier circuit yield is measured according to the following criteria. Evaluation was performed.
A (very good): The number of circuits that are not driven is 1 in 100 or less.
B (good): The number of circuits not driven is 2 or more and less than 5 out of 100.
C (possible): The number of circuits that are not driven is 5 or more and less than 10 out of 100.
D (impossible): The number of circuits that are not driven is 10 or more out of 100.

Synthesis Example 1: Synthesis of polysiloxane (PS-01) to which inorganic particles are bound 10.90 g (0.08 mol) of methyltrimethoxysilane (MeOH) and 3-trimethoxysilylpropylsuccinic acid anhydride (SucSi) are placed in a three-mouth flask. ) Is 5.25 g (0.02 mol), 1-naphthyltrimethoxysilane (NapSi) is 24.84 g (0.10 mol), and 20.6% by mass of titanium oxide-silicon oxide composite particle methanol dispersion is “Opto”. Lake (registered trademark) "TR-550 (manufactured by Nikki Catalyst Kasei Co., Ltd.) has a particle content of 100 parts by mass with respect to 100 parts by mass of 133.68 g (mass (27.54 g) when fully condensed organosilanes). ), Diacetone alcohol (DAA, boiling point 168 ° C.) was charged in 102.28 g, and 0.205 g of phosphoric acid (0.50% by mass with respect to the charged monomer) was dissolved in 11.16 g of water while stirring at room temperature. The aqueous solution was added over 10 minutes. Then, the flask was immersed in an oil bath at 40 ° C. and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. The internal temperature of the solution reached 100 ° C. 1 hour after the start of the temperature rise, and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.). The resin solution obtained by heating and stirring was cooled in an ice bath, and then 2% by weight of each of an anion exchange resin and a cation exchange resin was added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a solution of polysiloxane (PS-01) to which inorganic particles were bound. During the temperature rise and heating and stirring, nitrogen was flowed at 0.05 liter (liter) / min. A total of 121.19 g of methanol and water, which are by-products, were distilled off during the reaction. The solid content concentration of the obtained solution PS-01 of the polysiloxane to which the inorganic particles were bonded was 33% by mass.

Synthesis Example 2: Synthesis of polysiloxane (PS-02)
10.90 g (0.08 mol) of methyltrimethoxysilane (MeSi), 5.25 g (0.02 mol) of 3-trimethoxysilylpropyl succinic anhydride (SucSi), 1-naphthyltrimethoxysilane (NapSi) 24.84 g (0.10 mol) was dissolved in 64.26 g of propylene glycol monobutyl ether (boiling point: 170 ° C.), and 11.16 g of water and 0.205 g of phosphoric acid were added thereto with stirring. The obtained solution was heated at a bath temperature of 105 ° C. for 2 hours, the internal temperature was raised to 70 ° C., and a component mainly composed of methanol produced as a by-product was distilled off. Next, the bath temperature was heated at 130 ° C. for 2.0 hours, the internal temperature was raised to 110 ° C., and a component mainly composed of water and propylene glycol monobutyl ether was distilled off. The resin solution obtained by heating and stirring was cooled in an ice bath, and then 2% by weight of each of an anion exchange resin and a cation exchange resin was added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution having a solid content concentration of 36.0 wt%.

Synthesis Example 3: Synthesis of Polysiloxane (PS-03)
Methyltrimethoxysilane 61.29 g (0.09 mol), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 12.31 g (0.01 mol), and phenyltrimethoxysilane 99.15 g (0.10) Mol) was dissolved in 48.84 g of propylene glycol monobutyl ether (boiling point: 170 ° C.), and 10.98 g of water and 0.173 g of phosphoric acid were added thereto with stirring. The obtained solution was heated at a bath temperature of 105 ° C. for 2 hours, the internal temperature was raised to 90 ° C., and a component mainly composed of methanol produced as a by-product was distilled off. Next, the bath temperature was heated at 130 ° C. for 2.0 hours, the internal temperature was raised to 118 ° C., and a component mainly composed of water and propylene glycol monobutyl ether was distilled off. The resin solution obtained by heating and stirring was cooled in an ice bath, and then 2% by weight of each of an anion exchange resin and a cation exchange resin was added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution having a solid content concentration of 36.0 wt%.

Synthesis Example 4: Synthesis of naphthoquinone diazide compound (QD-01) Ph-cc-AP-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphtho under a dry nitrogen stream. 37.62 g (0.14 mol) of quinonediazide sulfonyl acid chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not exceed 35 ° C. After the dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound (QD-01) having the following structure.

Synthesis Example 5; Compound P1 (polymerizable component: polymer having a polymerizable unsaturated group)
Copolymerization ratio (weight basis): Ethyl acrylate (hereinafter "EA") / 2-ethylhexyl methacrylate (hereinafter "2-EHMA") / styrene (hereinafter "St") / glycidyl methacrylate (hereinafter "GMA") ) / Acrylic acid (hereinafter, "AA") = 20/40/20/5/15.

150 g of diethylene glycol monoethyl ether acetate (hereinafter, “DMEA”) was charged in a reaction vessel having a nitrogen atmosphere, and the temperature was raised to 80 ° C. using an oil bath. A mixture of 20 g of EA, 40 g of 2-EHMA, 20 g of St, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile and 10 g of DMEA was added dropwise thereto over 1 hour. did. After completion of the dropping, the polymerization reaction was further carried out for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. Subsequently, a mixture consisting of 5 g of GMA, 1 g of triethylbenzylammonium chloride and 10 g of DMEA was added dropwise over 0.5 hours. After completion of the dropping, an addition reaction was carried out for another 2 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and vacuum dried for 24 hours to obtain compound P1.

Synthesis Example 6; Compound P2 (polymerizable component: polymer having a polymerizable unsaturated group)
Copolymerization ratio (weight basis): Bifunctional epoxy acrylate monomer (epoxy ester 3002A; manufactured by Kyoeisha Chemical Co., Ltd.) / Bifunctional epoxy acrylate monomer (epoxy ester 70PA; manufactured by Kyoeisha Chemical Co., Ltd.) / GMA / St / AA = 20/40/5/20/15.

150 g of DMEA was charged in a reaction vessel having a nitrogen atmosphere, and the temperature was raised to 80 ° C. using an oil bath. A mixture of 20 g of epoxy ester 3002A, 40 g of epoxy ester 70PA, 20 g of St, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile and 10 g of DMEA over 1 hour. And dropped. After completion of the dropping, the polymerization reaction was further carried out for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. Subsequently, a mixture consisting of 5 g of GMA, 1 g of triethylbenzylammonium chloride and 10 g of DMEA was added dropwise over 0.5 hours. After completion of the dropping, an addition reaction was carried out for another 2 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and vacuum dried for 24 hours to obtain compound P2.

Synthesis Example 7; Compound P3 which is a urethane-modified compound of Compound P2 (polymerizable component: polymer having a polymerizable unsaturated group)
100 g of diethylene glycol monoethyl ether acetate (hereinafter, “DMEA”) was charged in a reaction vessel having a nitrogen atmosphere, and the temperature was raised to 80 ° C. using an oil bath. To this, a mixture consisting of 10 g of the photosensitive component P2, 3.5 g of n-hexyl isocyanate and 10 g of DMEA was added dropwise over 1 hour. After completion of the dropping, the reaction was carried out for another 3 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further vacuum dried for 24 hours to obtain compound P3 having a urethane bond.

Preparation Example 1: Preparation of semiconductor solution Poly (3-hexylthiophene) (P3HT) (manufactured by Aldrich Co., Ltd.) Add CNT (manufactured by CNI, single-walled CNT, 95% purity) to 2.0 mg of a 10 ml solution of chloroform. Add 0 mg, and while cooling with ice, use an ultrasonic homogenizer (VCX-500 manufactured by Tokyo Rika Kikai Co., Ltd.) to ultrasonically stir at 20% output for 4 hours, and CNT dispersion A (CNT complex concentration with respect to solvent 0.96 g). / L) was obtained.

Next, a semiconductor solution for forming the semiconductor layer was prepared. The CNT dispersion liquid A was filtered using a membrane filter (pore diameter 10 μm, diameter 25 mm, omnipore membrane manufactured by Millipore) to remove CNT complexes having a length of 10 μm or more. After adding 5 ml of o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) to the obtained filtrate, chloroform, which is a low boiling point solvent, was distilled off using a rotary evaporator, and the solvent was replaced with o-dichlorobenzene. Then, the CNT dispersion liquid B was obtained. 3 mL of o-dichlorobenzene was added to 1 ml of the CNT dispersion liquid B to prepare a semiconductor solution (CNT complex concentration 0.03 g / l with respect to the solvent).

Preparation Example 2: Preparation of conductive paste 1.6 g of compound P1 and 0.4 g of compound P3 in a 100 ml clean bottle, 0.4 g of photopolymerization initiator OXE-01 (manufactured by BASF Japan Co., Ltd.), acid generator SI-110. (Sankyo Chemical Co., Ltd.) 0.06 g and diacetone alcohol (Sankyo Chemical Co., Ltd.) 38 g are added, and the rotation-revolution vacuum mixer "Awatori Rentaro" (registered trademark) (ARE-310; (Manufactured by Shinky Co., Ltd.) was mixed to obtain 40.86 g (solid content 4.0% by weight) of a photosensitive resin solution. 20.0 g of the obtained photosensitive resin solution and 5.0 g of Ag particles having a volume average particle diameter of 0.5 μm are mixed and kneaded using a three-roller “EXAKT M-50” (trade name, manufactured by EXAKT). , 25 g of conductive paste was obtained.

Example 1
16.36 g of polysiloxane solution (PS-01, polymer A) to which inorganic particles are bonded, 0.60 g of Araster 700 (Polymer B, styrene / maleic acid half ester copolymer, manufactured by Arakawa Chemical Industry Co., Ltd.) (polymer) The mixed weight ratio of A and polymer B is 90:10), 0.54 g of quinonediazide compound (QD-01), 300 ppm of BYK-333 (polysiloxane-based surfactant, manufactured by Big Chemie Japan Co., Ltd.), DAA33. 04 g was mixed under a yellow lamp and stirred to obtain a uniform solution, which was then filtered through a 0.20 μm filter to obtain an insulating material solution (solid content concentration: 12% by mass).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2).
Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). Further, the FET was produced by the method described in (4), the film thickness of the gate insulating film was evaluated by the method described in (1), and the FET characteristics were evaluated by the method described in (7).
Further, a rectifier circuit was produced by the method described in (5), the film thickness of the insulating film was evaluated by the method described in (1), and the yield of the rectifier circuit was evaluated by the method described in (8). The results are shown in Tables 1-4.

Example 2
Insulating material solution in the same manner as in Example 1 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 13.64 g, Alaster 700 to 1.50 g, and DAA to 34.86 g. (Solid content concentration 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 75:25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 3
Insulating material solution in the same manner as in Example 1 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 9.09 g, Alaster 700 was changed to 3.00 g, and DAA was changed to 37.91 g. (Solid content concentration 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 50:50).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 4
Insulating material solution in the same manner as in Example 1 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 17.27 g, Alaster 700 to 0.30 g, and DAA to 32.42 g. (Solid content concentration 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 95: 5).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 5
1. Instead of Araster 700, WR-301 (made by ADEKA Co., Ltd., propylene glycol monomethyl ether acetate solution, 44.5% by weight, polyester having a carboxylic acid residue represented by the general formula (5), polymer B) 1. An insulating material solution (solid content concentration 12% by mass) was obtained in the same manner as in Example 1 except that 35 g was used and the DAA was changed to 32.29 g (mixed weight ratio of polymer A and polymer B was 90:10). ).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). Further, the FET was produced by the method described in (4), the film thickness of the gate insulating film was evaluated by the method described in (1), and the FET characteristics were evaluated by the method described in (7). Further, a rectifier circuit was produced by the method described in (5), the film thickness of the insulating film was evaluated by the method described in (1), and the yield of the rectifier circuit was evaluated by the method described in (8). The results are shown in Tables 1-4.

Example 6
Insulating material in the same manner as in Example 5 except that the solution of polysiloxane (PS-01) to which inorganic particles were bonded was changed to 13.64 g, WR-301 was changed to 3.37 g, and DAA was changed to 32.99 g. A solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 75:25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 7
Insulating material in the same manner as in Example 5 except that the solution of polysiloxane (PS-01) to which inorganic particles were bonded was changed to 9.09 g, WR-301 was changed to 6.74 g, and DAA was changed to 34.17 g. A solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 50:50).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 8
Insulating material in the same manner as in Example 5 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 17.27 g, WR-301 to 0.67 g, and DAA to 32.05 g. A solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 95: 5).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 9
Instead of Araster 700, 1.67 g of the polysiloxane solution (PS-02, Polymer B) synthesized in Synthesis Example 2 was used, and the polysiloxane solution (PS-01) to which the inorganic particles were bound was added to 18.00 g, and DAA was added. An insulating material solution (solid content concentration: 12% by mass) was obtained in the same manner as in Example 1 except that the weight was changed to 30.33 g (mixed weight ratio of polymer A and polymer B was 90:10).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). Further, the FET was produced by the method described in (4), the film thickness of the gate insulating film was evaluated by the method described in (1), and the FET characteristics were evaluated by the method described in (7). Further, a rectifier circuit was produced by the method described in (5), the film thickness of the insulating film was evaluated by the method described in (1), and the yield of the rectifier circuit was evaluated by the method described in (8). The results are shown in Tables 1-4.

Example 10
Example 9 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 13.64 g, the polysiloxane solution (PS-02) was changed to 4.17 g, and the DAA was changed to 32.20 g. In the same manner, an insulating material solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 75:25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 11
Example 9 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 9.09 g, the polysiloxane solution (PS-02) was changed to 8.33 g, and the DAA was changed to 32.58 g. In the same manner, an insulating material solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 50:50).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 12
Example 9 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 17.27 g, the polysiloxane solution (PS-02) was changed to 0.83 g, and the DAA was changed to 31.89 g. In the same manner, an insulating material solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 95: 5).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 13
Instead of Araster 700, 1.67 g of the polysiloxane solution (PS-03, Polymer B) synthesized in Synthesis Example 3 was used, and the polysiloxane solution (PS-01) to which the inorganic particles were bound was added to 18.00 g, and DAA was added. An insulator solution (solid content concentration: 12% by mass) was obtained in the same manner as in Example 1 except that the weight was changed to 30.33 g (mixed weight of polymer A and polymer B). The ratio is 90:10).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). Further, the FET was produced by the method described in (4), the film thickness of the gate insulating film was evaluated by the method described in (1), and the FET characteristics were evaluated by the method described in (7). Further, a rectifier circuit was produced by the method described in (5), the film thickness of the insulating film was evaluated by the method described in (1), and the yield of the rectifier circuit was evaluated by the method described in (8). The results are shown in Tables 1-4.

Example 14
Example 13 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 13.64 g, the polysiloxane solution (PS-03) was changed to 4.17 g, and the DAA was changed to 32.20 g. In the same manner, an insulating material solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 75:25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 15
Example 9 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 9.09 g, the polysiloxane solution (PS-03) was changed to 8.33 g, and the DAA was changed to 32.58 g. In the same manner, an insulating material solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 50:50).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 16
Example 9 except that the polysiloxane solution (PS-01) to which the inorganic particles were bonded was changed to 17.27 g, the polysiloxane solution (PS-03) was changed to 0.83 g, and the DAA was changed to 31.89 g. In the same manner, an insulating material solution (solid content concentration: 12% by mass) was obtained (mixed weight ratio of polymer A and polymer B was 95: 5).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 17
An insulating material solution (solid content concentration 12% by mass) was obtained in the same manner as in Example 2 except that the surfactant BYK333 300 ppm was changed to DFX-18 150 ppm (the mixed weight ratio of the polymer A and the polymer B was 75). : 25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 18
An insulating material solution (solid content concentration 12% by mass) was obtained in the same manner as in Example 6 except that the surfactant BYK333 300 ppm was changed to DFX-18 150 ppm (the mixed weight ratio of the polymer A and the polymer B was 75). : 25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Example 19
An insulating material solution (solid content concentration 12% by mass) was obtained in the same manner as in Example 10 except that the surfactant BYK333 300 ppm was changed to DFX-18 150 ppm (the mixed weight ratio of the polymer A and the polymer B was 75). : 25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). Further, the FET was produced by the method described in (4), the film thickness of the gate insulating film was evaluated by the method described in (1), and the FET characteristics were evaluated by the method described in (7). Further, a rectifier circuit was produced by the method described in (5), the film thickness of the insulating film was evaluated by the method described in (1), and the yield of the rectifier circuit was evaluated by the method described in (8). The results are shown in Tables 1-4.

Example 20
An insulating material solution (solid content concentration 12% by mass) was obtained in the same manner as in Example 14 except that the surfactant BYK333 300 ppm was changed to DFX-18 150 ppm (the mixed weight ratio of the polymer A and the polymer B was 75). : 25).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). The results are shown in Tables 1 and 2.

Comparative Example 1
18.18 g of a polysiloxane solution (PS-01) to which inorganic particles are bound, 0.54 g of a quinonediazide compound (QD-01), and 300 ppm of BYK-333 (polysiloxane-based surfactant, manufactured by Big Chemie Japan Co., Ltd.). , DAA 31.82 g was mixed under a yellow lamp, stirred to obtain a uniform solution, and then filtered through a 0.20 μm filter to obtain an insulating material solution (solid content concentration: 12% by mass).

Using the obtained insulator solution, the relative permittivity of the insulator was measured by the method described in (2). Further, a capacitor was produced by the method described in (3), the film thickness of the dielectric film was evaluated by the method described in (1), and the short circuit rate was evaluated by the method described in (6). Further, the FET was produced by the method described in (4), the film thickness of the gate insulating film was evaluated by the method described in (1), and the FET characteristics were evaluated by the method described in (7). Further, a rectifier circuit was produced by the method described in (5), the film thickness of the insulating film was evaluated by the method described in (1), and the yield of the rectifier circuit was evaluated by the method described in (8). The results are shown in Tables 1-4.

Comparative Example 2: Preparation of Insulator Solution An insulator solution was prepared in the same manner as in Example 1 except that polystyrene (manufactured by Sigma-Aldrich) was used instead of Araster 700, but titanium oxide particles were precipitated. Therefore, a uniform solution could not be obtained.

11, 31, 61, 71 Gate electrodes 12, 62 Gate insulating films 13, 35, 64, 75 Source electrodes 14, 34, 63, 74 Semiconductor layers 15, 36, 65, 76 Drain electrodes 38, 78 Wiring 39, 79 vias 100, 200, 300, 400, 500, 600, 700 Insulating base material 301, 701 FET element 302, 702 Capulator element 21, 32, 51, 72 Lower electrode 22, 52 Dielectric film 23, 37, 53, 77 Upper electrode 33 , 33A, 33B, 73 Insulation film 40 Antenna 41 Demodulation circuit 42 Control circuit 43 Modulation circuit 44 Storage circuit 45 Power supply generator

Claims (13)

at least,
(A) Polymer A: A polymer in which a polymer is bonded to inorganic particles having a herodoxy group on the surface.
(B) Polymer B: A polymer that is not bonded to inorganic particles and has a functional group capable of forming a hydrogen bond with a hydroxy group on the surface of the inorganic particles contained in the polymer A, and (c) a resin containing a solvent. Composition. The resin composition according to claim 1, wherein the polymer contained in the polymer A contains a polysiloxane. The resin composition according to claim 1 or 2, wherein the polymer contained in the polymer A has at least a structural unit represented by the general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group or an alkenyl group. R ² is a hydrogen atom, an alkyl group or a cycloalkyl group. It represents a group or a silyl group. M represents 0 or 1. A ¹ represents an organic group containing at least two carboxyl group, sulfo group, thiol group, phenolic hydroxyl group or derivatives thereof. the carboxyl group, a sulfo group when a two by cyclocondensation structure of thiol groups and phenolic hydroxyl groups, a ¹ represents an organic group having at least one said ring fused structure.) The resin composition according to any one of claims 1 to 3, wherein the inorganic particles contained in the polymer A are inorganic oxide particles. One of claims 1 to 4, wherein the polymer B has at least one functional group selected from the group consisting of a carboxyl group, a sulfo group, a phosphoric acid group, a mercapto group, a hydroxyl group, an epoxy group and a derivative thereof. The resin composition described. The polymer B contains a polysiloxane having a structural unit represented by the general formula (4), a resin having a phenolic hydroxyl group, a polyester having a carboxylic acid residue represented by the general formula (5), and polymaleic acid. The resin composition according to any one of claims 1 to 5, which comprises at least one selected from the group consisting of the derivatives.

(In the general formula (4), R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group or an alkenyl group. R ⁶ is a hydrogen atom, an alkyl group or a cycloalkyl group. It represents a group or a silyl group. N represents 0 or 1. A ² represents an organic group containing at least one carboxyl group, sulfo group, thiol group, phenolic hydroxyl group, epoxy group or a derivative thereof. When the derivative has a cyclic condensation structure consisting of any two of the carboxyl group, sulfo group, thiol group and phenolic hydroxyl group, A ² represents an organic group having at least one cyclic condensation structure. )

(In the general formula (5), R ⁷ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group, an alkenyl group, or an organic group represented by the general formula (6). .)

(In the general formula (6), R ⁸ represents a hydroxyl group, an alkoxy group, or a functional group represented by the general formula (7).)

(In the general formula (7), R ⁹ represents a functional group represented by an alkylene group or an oxyalkylene group. R ¹⁰ represents a hydrogen atom or a methyl group.) The invention according to any one of claims 1 to 6, wherein the content of the polymer B is 8 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the total of (a) polymer A and (b) polymer B. Resin composition. The resin composition according to any one of claims 1 to 7, further comprising a fluorine-based surfactant in the resin composition. A method for manufacturing an element, which comprises the following (step 1) to (step 3).
(Step 1) Step of forming a conductive pattern to be a lower electrode on a substrate (Step 2) The resin composition according to any one of claims 1 to 8 is applied onto a substrate on which the conductive pattern is formed. And drying to obtain a coating film (step 3) A step of forming a conductive pattern as an upper electrode on the coating film. A method for manufacturing an element, which comprises the following (step 1') to (step 3').
(Step 1') Step of forming a conductive pattern to be a lower electrode on a substrate (Step 2') A photosensitive resin composition containing the resin composition according to any one of claims 1 to 8 and a photosensitive organic component. The material is applied and dried on the substrate on which the conductive pattern is formed to obtain a coating film, and then the coating film is irradiated with active chemical rays via a photomask and developed to develop the conductive pattern. Step of forming a dielectric pattern having an opening on the top (Step 3') A step of forming a conductive pattern to be an upper electrode on the dielectric pattern. The method for manufacturing an element according to claim 9 or 10, wherein the element is a capacitor. The method for manufacturing an element according to claim 9 or 10, wherein the element is a field effect transistor. The method for manufacturing an element according to claim 12, further comprising a step of applying and drying a semiconductor solution containing carbon nanotubes on the coating film to obtain a semiconductor film.

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