WO2019097978A1

WO2019097978A1 - N-type semiconductor element, method for producing n-type semiconductor element, wireless communication device and product tag

Info

Publication number: WO2019097978A1
Application number: PCT/JP2018/039728
Authority: WO
Inventors: 磯貝和生; 脇田潤史; 村瀬清一郎
Original assignee: 東レ株式会社
Priority date: 2017-11-20
Filing date: 2018-10-25
Publication date: 2019-05-23
Also published as: JPWO2019097978A1; JP6954310B2; TW201925373A

Abstract

The purpose of the present invention is to provide an n-type semiconductor element which has excellent stability by a simple process. The gist of the present invention is an n-type semiconductor element which is provided with a substrate, a source electrode, a drain electrode, a gate electrode, a semiconductor layer that is in contact with the source electrode and the drain electrode, a gate insulating layer that insulates the semiconductor layer from the gate electrode, and a second insulating layer which is in contact with the semiconductor layer on the opposite side of the gate insulating layer with respect to the semiconductor layer, and which is characterized in that: the semiconductor layer contains nanocarbons; and the second insulating layer contains a polymer that has a structure represented by general formula (1) in at least some of the side chains.

Description

N-type semiconductor device, method of manufacturing n-type semiconductor device, wireless communication device and product tag

The present invention relates to an n-type semiconductor device and a method of manufacturing the same, and also relates to a wireless communication device and a product tag using the n-type semiconductor device.

In recent years, development of a wireless communication system using RFID (Radio Frequency IDentification) technology as a noncontact tag has been advanced. In the RFID system, wireless communication is performed between a wireless transceiver called a reader / writer and an RFID tag.

RFID tags are expected to be used in various applications such as physical distribution management, product management, shoplifting prevention, etc., and have been introduced in some applications such as IC cards such as traffic cards and product tags. The RFID tag has an IC chip and an antenna. An antenna provided in the RFID tag receives a carrier wave transmitted from the reader / writer, and a drive circuit in the IC chip operates.

RFID tags are expected to be used in all types of products. For that purpose, it is necessary to reduce the manufacturing cost of the RFID tag. Therefore, in the RFID tag manufacturing process, it has been considered to use a flexible and inexpensive process using coating and printing technology in order to break away from processes using vacuum and high temperature.

For example, in a transistor in a driver circuit in an IC chip, it is conceivable to use an organic semiconductor to which an inkjet technique or a screening technique can be applied as a material of a semiconductor layer. Therefore, field effect transistors (hereinafter referred to as FETs) using carbon nanotubes (CNTs) or organic semiconductors have been actively studied in place of conventional inorganic semiconductors (see, for example, Patent Document 1).

The driver circuit in the IC chip is generally composed of a complementary circuit composed of a p-type FET and an n-type FET in order to reduce the power consumption. However, FETs using CNTs (hereinafter referred to as CNT-FETs) are generally known to exhibit the characteristics of p-type semiconductor devices in the atmosphere. Therefore, conversion of the characteristics of the CNT-FET into an n-type semiconductor device is studied by vacuum heating the CNT-FET or doping the CNT with oxygen, potassium or the like (for example, Patent Document 2, Non-Patent Document 1).

WO 2009/139339 pamphlet U.S. Patent Application Publication No. 2003/122133

Patent Document 2 discusses a method of doping CNTs with oxygen or potassium ions to convert them into n-type semiconductor devices. However, there is a problem that oxygen is difficult to separate as an element and potassium ion is difficult to handle.

In Non-Patent Document 1, after protecting the pattern of FET using CNT by photolithography technology, a method of performing vacuum heat treatment at 200 ° C. for 10 hours to convert it into an n-type semiconductor device is studied. However, it is necessary to perform high temperature processing in a vacuum state for a long time, and there is a problem that the process is prolonged and the manufacturing cost is increased.

In addition, CNT-FETs manufactured by techniques as described in Patent Document 2 and Non-patent Document 1 have problems that the n-type semiconductor characteristics are insufficient and the semiconductor characteristics change due to humidity. The

An object of the present invention is to provide an n-type semiconductor device having high n-type semiconductor characteristics and excellent stability by a simple process.

In order to solve the above-mentioned subject, the present invention has the following composition.
That is, the present invention
A substrate,
A source electrode, a drain electrode and a gate electrode,
A semiconductor layer in contact with the source electrode and the drain electrode;
A gate insulating layer which insulates the semiconductor layer from the gate electrode;
An n-type semiconductor element comprising: a second insulating layer in contact with the semiconductor layer on the side opposite to the gate insulating layer with respect to the semiconductor layer;
The semiconductor layer contains nanocarbon,
The second insulating layer is an n-type semiconductor device including a polymer having a structure represented by the general formula (1) in at least a part of a side chain.

In the general formula (1), R ¹ and R ² are each independently composed of one or more atoms selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom Group is shown. R ³ and R ⁴ each independently represent a hydrogen atom or a group represented by the above general formula (2).

In the general formula (2), R ⁵ to R ⁷ are each independently composed of one or more atoms selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom Group is shown.

According to the present invention, an n-type semiconductor device excellent in stability can be obtained. Further, according to the manufacturing method of the present invention, the n-type semiconductor device can be obtained by a simple process. Further, a wireless communication device and a product tag using the semiconductor element can be provided.

A schematic cross-sectional view showing an n-type semiconductor device which is one of the embodiments of the present invention A schematic cross-sectional view showing an n-type semiconductor device which is one of the embodiments of the present invention A schematic cross-sectional view showing an n-type semiconductor device which is one of the embodiments of the present invention A schematic cross-sectional view showing an n-type semiconductor device which is one of the embodiments of the present invention Sectional view showing a manufacturing process of an n-type semiconductor device which is one of the embodiments of the present invention FIG. 5A is a sectional view showing the manufacturing process of the n-type semiconductor device which is one of the embodiments of the present invention from FIG. 5A. A block diagram showing an example of a wireless communication apparatus using an n-type semiconductor device according to an embodiment of the present invention

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of an n-type semiconductor device, a method of manufacturing an n-type semiconductor device, a wireless communication device and a product tag according to the present invention will be described in detail below. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented according to the purpose and application.

<N-type semiconductor device>
In an n-type semiconductor device according to an embodiment of the present invention, a base material, a source electrode, a drain electrode and a gate electrode, a semiconductor layer in contact with the source electrode and the drain electrode, and the semiconductor layer are insulated from the gate electrode. An n-type semiconductor device comprising: a gate insulating layer; and a second insulating layer in contact with the semiconductor layer on the opposite side of the semiconductor layer from the gate insulating layer, wherein the semiconductor layer contains nanocarbon And the second insulating layer contains a polymer having a structure represented by the general formula (1) in at least a part of a side chain.

FIG. 1 is a schematic cross-sectional view showing a first example of a semiconductor device according to an embodiment of the present invention. A gate electrode 2 formed on an insulating base material 1, a gate insulating layer 3 covering it, a source electrode 5 and a drain electrode 6 provided thereon, and a semiconductor layer provided between the electrodes 4 and a second insulating layer 8 covering the semiconductor layer. The semiconductor layer 4 contains nanocarbon 7.

This structure is a so-called bottom gate bottom contact structure in which the gate electrode is disposed below the semiconductor layer and the source electrode and the drain electrode are disposed on the lower surface of the semiconductor layer.

FIG. 2 is a schematic cross-sectional view showing a second example of the semiconductor device according to the embodiment of the present invention. A gate electrode 2 formed on an insulating substrate 1, a gate insulating layer 3 covering it, a semiconductor layer 4 provided thereon, and a source electrode 5 and a drain electrode 6 formed thereon , And the second insulating layer 8 provided thereon. The semiconductor layer 4 contains nanocarbon 7.

This structure is a so-called bottom gate top contact structure in which the gate electrode is disposed below the semiconductor layer, and the source electrode and the drain electrode are disposed on the upper surface of the semiconductor layer.

The structure of the semiconductor device according to the embodiment of the present invention is not limited to these. Further, the following description is common regardless of the structure of the semiconductor element unless otherwise noted.

(Base material)
The substrate may be made of any material as long as at least the surface on which the electrode system is disposed is insulating. As a base material, for example, a base material made of an inorganic material such as silicon wafer, glass, sapphire, alumina sintered body, polyimide, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyvinyl terephthalate, polyvinylidene fluoride, polysiloxane, polyvinyl phenol (PVP) Preferred are substrates made of an organic material such as polyester, polycarbonate, polysulfone, polyethersulfone, polyethylene, polyphenylene sulfide, polyparaxylene and the like.

In addition, as the base material, for example, a base material in which a PVP film is formed on a silicon wafer, or a base material in which a polysiloxane film is formed on polyethylene terephthalate may be used.

The substrate preferably has a low water vapor permeability. The water vapor permeability of the substrate is preferably 20 g / (m ² · 24 h) or less. More preferably, it is 10 g / (m ² · 24 h) or less, still more preferably 1 g / (m ² · 24 h) or less.

In the present invention, the water vapor permeability of the base material and the barrier layer described later is measured based on JIS K 7129 2008 (how to determine the water vapor permeability of plastic films and sheets).

(electrode)
The material used for the gate electrode, the source electrode and the drain electrode may be any conductive material which can be generally used as an electrode. For example, conductive metal oxides such as tin oxide, indium oxide, and indium tin oxide (ITO); platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, Metals such as calcium, magnesium, palladium, molybdenum, amorphous silicon, polysilicon and their alloys; Inorganic conductive substances such as copper iodide, copper sulfide; polythiophene, polypyrrole, polyaniline; polyethylenedioxythiophene and polystyrene sulfonic acid Examples include, but are not limited to, complexes and the like; conductive polymers and the like whose conductivity is improved by doping with iodine and the like; carbon materials and the like; and materials containing an organic component and a conductor, and the like.

These electrode materials may be used alone, but may be used by laminating or mixing a plurality of materials.

Among them, the electrode has an organic component and a conductor because the flexibility of the electrode is increased, the adhesion to the base material and the gate insulating layer is good even when bent, and the electrical connection to the wiring and the semiconductor layer is good. It is preferable to contain.

The organic component is not particularly limited, and monomers, oligomers, polymers, photopolymerization initiators, plasticizers, leveling agents, surfactants, silane coupling agents, antifoaming agents, pigments and the like can be mentioned. From the viewpoint of improving the bending resistance of the electrode, the organic component is preferably an oligomer or a polymer.

The oligomer or polymer is not particularly limited, and an acrylic resin, an epoxy resin, a novolak resin, a phenol resin, a polyimide precursor, a polyimide or the like can be used. Among these, an acrylic resin is preferable from the viewpoint of crack resistance when the electrode is bent. It is presumed that this is because the glass transition temperature of the acrylic resin is 100 ° C. or less, and the conductive film is softened at the time of heat curing to increase the bonding between the conductive particles.

An acrylic resin is a resin containing a structure derived from at least an acrylic monomer in a repeating unit. Specific examples of the acrylic monomer include all compounds having a carbon-carbon double bond, and preferably
Methyl acrylate, acrylic acid, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl acrylate, i-butyl acrylate, i-propane acrylate, glycidyl acrylate, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, Nn-n- Butoxymethyl acrylamide, N-isobutoxy methyl acrylamide, butoxy triethylene glycol acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, iso Octyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy ethylene glycol acrylate , Methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, Acrylic monomers such as benzyl mercaptan acrylate and methacrylates replaced by methacrylates;
Styrenes such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene and the like;
γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone;
Etc.

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

Any conductor may be used as the conductor, as long as it can be generally used as an electrode, but the conductive material is composed entirely or in part of the conductive material, and the particles themselves are conductive particles having conductivity. Is preferred. By using conductive particles as a conductor, irregularities are formed on the surface of the electrode including it. When the gate insulating film enters the unevenness, an anchor effect is generated and adhesion between the electrode and the gate insulating film is further improved. By improving the adhesion between the electrode and the gate insulating film, there is an effect of improving the bending resistance of the electrode and an effect of suppressing the fluctuation of the electrical characteristics when a voltage is repeatedly applied to the semiconductor element. These effects further improve the reliability of the semiconductor device.

Examples of conductive materials suitable for the conductive particles include gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminum, tungsten, molybdenum, carbon and the like. More preferable conductive particles are conductive particles containing at least one element selected from the group consisting of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminum and carbon. These conductive particles may be used alone, may be used as an alloy, or may be used as mixed particles.

Among these, particles of gold, silver, copper or platinum are preferable from the viewpoint of conductivity. Among them, silver particles are more preferable from the viewpoint of cost and stability.

0.01 micrometer or more and 5 micrometers or less are preferable, and, as for the average particle diameter of the electroconductive particle in an electrode, 0.01 micrometer or more and 2 micrometers or less are more preferable. When the average particle diameter of the conductive particles is 0.01 μm or more, the contact probability between the conductive particles is improved, and the specific resistance value of the manufactured electrode can be reduced, and the disconnection probability is lowered. Can. In addition, when the average particle diameter of the conductive particles is 5 μm or less, it becomes an electrode having high bending resistance. In addition, when the average particle diameter of the conductive particles is 2 μm or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the electrode are further improved.

In the present invention, the average particle diameter of the conductive particles in the electrode is a value measured by the following method. The cross section of the electrode is observed at a magnification of 10000 using a scanning electron microscope. Each particle diameter is measured for 100 particles randomly selected from the obtained image, and the value of the arithmetic mean is taken as the average particle diameter. The particle diameter is the particle diameter when the particle shape is spherical. When the shape of the particles is other than spherical, the average value of the maximum width and the minimum width among the widths observed with an electron microscope is calculated as the particle diameter of the particle for a certain particle.

The amount of the conductor in the electrode is preferably 70 wt% or more and 95 wt% or less of the electrode, and the lower limit is 80 wt% or more, and the upper limit is 90 wt% or less. By being in this range, the specific resistance value of the electrode can be reduced, and the disconnection probability can be reduced.

In addition, the width and thickness of each of the gate electrode, the source electrode and the drain electrode, and the distance between the source electrode and the drain electrode can be designed to any value. For example, the electrode width is preferably 10 μm to 10 mm, the thickness of the electrode is preferably 0.01 μm to 100 μm, and the distance between the source electrode and the drain electrode is preferably 1 μm to 1 mm, respectively, but not limited thereto.

The method for forming the electrode is not particularly limited, and methods using known techniques such as resistance heating evaporation, electron beam, sputtering, plating, chemical vapor deposition (CVD), ion plating coating, inkjet, printing, etc. Can be mentioned. In addition, as another example of a method of forming an electrode, a paste containing an organic component and a conductor is subjected to spin coating, blade coating, slit die coating, screen printing, bar coating, molding, printing transfer, immersion The method of apply | coating on an insulating substrate by well-known techniques, such as a pulling-up method, drying using oven, a hotplate, infrared rays etc., etc. is mentioned.

In addition, as a method of forming an electrode pattern, the electrode thin film prepared by the above method may be patterned into a desired shape by a known photolithography method or the like, or desired at the time of deposition or sputtering of an electrode material. The pattern may be formed through a mask of a shape.

(Gate insulating layer)
Materials used for the gate insulating layer are not particularly limited, but inorganic materials such as silicon oxide and alumina; organic high polymers such as polyimide, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyvinylidene fluoride, polysiloxane, polyvinyl phenol (PVP) and the like A molecular material; or a mixture of inorganic material powder and organic material can be mentioned.
Among them, those containing an organic compound containing a bond of silicon and carbon are preferable.

Examples of the organic compound include a silane compound represented by the general formula (9), an epoxy group-containing silane compound represented by the general formula (10), a condensate thereof, or a polysiloxane containing these as a copolymerization component. . Among these, polysiloxane is more preferable from the viewpoint of high insulation and low-temperature curing.

R ¹⁴ _m Si (OR ¹⁵ ) _4-m (9)
Here, R ¹⁴ represents a hydrogen atom, an alkyl group, a heterocyclic group, an aryl group or an alkenyl group. When a plurality of R ¹⁴ are present, each R ¹⁴ may be the same or different. R ¹⁵ represents a hydrogen atom, an alkyl group, an acyl group or an aryl group. When a plurality of R ¹⁵ are present, each R ¹⁵ may be the same or different. m is an integer of 1 to 3;

R ¹⁶ _n R ¹⁷ _l Si (OR ¹⁸ ) _4-n-l (10)
Here, R ¹⁶ represents an alkyl group having one or more epoxy groups in part of the chain. When a plurality of R ¹⁶ are present, each R ¹⁶ may be the same or different. R ¹⁷ represents a hydrogen atom, an alkyl group, a heterocyclic group, an aryl group or an alkenyl group. When a plurality of R ¹⁷ are present, each R ¹⁷ may be the same or different. R ¹⁸ represents a hydrogen atom, an alkyl group, an acyl group or an aryl group. When a plurality of R ¹⁸ is present, each R ¹⁸ may be the same or different. l is an integer of 0 to 2, and n is 1 or 2. However, l + n ≦ 3.

The description of the alkyl group, the acyl group and the aryl group in R ¹⁴ to R ¹⁸ is the same as the description on R ¹⁹ to R ²⁴ described later.

The heterocyclic group in R ¹⁴ and R ¹⁷ is, for example, a group derived from an aliphatic ring having an atom other than carbon in the ring, such as pyran ring, piperidine ring, amido ring, etc., and this has a substituent It may or may not have. The carbon number of the heterocyclic group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The alkenyl group in R ¹⁴ and R ¹⁷ is, for example, an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group or a butadienyl group, which may have a substituent even if it has a substituent. You do not have to. The carbon number of the alkenyl group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The alkyl group having an epoxy group in a part of the chain, which is contained in R ¹⁶ , has a three-membered ring ether structure formed by combining two adjacent carbon atoms with one oxygen atom as a part of the chain. It shows an alkyl group. As such an alkyl group, the following two alkyl groups are mentioned. One is a case where two adjacent carbon atoms contained in the main chain which is the longest continuous portion of carbon atoms in the alkyl group are used. The other is the case where two adjacent carbon atoms contained in a portion other than the main chain, so-called side chain, are used in the alkyl group.

By introducing a silane compound represented by the general formula (9) as a copolymerization component of polysiloxane, it is possible to maintain high transparency in the visible light region while having high insulation and chemical resistance and within the insulating film. An insulating film with few traps can be formed.

In addition, when at least one of the m R ¹⁴ in the general formula (9) is an aryl group, the flexibility of the insulating film is improved, and the generation of a crack can be prevented, which is preferable.

Specific examples of the silane compound represented by the general formula (9) include vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and propyltritrisilane. Methoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, benzyltrimethoxysilane, α-naphthyltrimethoxysilane, β- Naphthyltrimethoxysilane, trifluoroethyltrimethoxysilane, trimethoxysilane, p-trifluorophenyltriethoxysilane and the like can be mentioned.

Moreover, it is more preferable to combine 2 or more types of silane compounds represented by General formula (9). Among them, a combination of a silane compound having an alkyl group and a silane compound having an aryl group is particularly preferable because high insulating properties and flexibility for crack prevention can be achieved at the same time.

Specific examples of the epoxy group-containing silane compound represented by the general formula (10) include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ- Glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, Examples thereof include β- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane and the like.

The gate insulating layer preferably further contains a metal compound containing a bond of a metal atom and an oxygen atom. Such metal compounds are not particularly limited, and examples thereof include metal oxides, metal hydroxides and the like. The metal atom contained in the metal compound is not particularly limited as long as it forms a metal chelate. As a metal atom, magnesium, aluminum, titanium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, zirconium, ruthenium, palladium, indium, hafnium, platinum etc. are mentioned, for example. Among them, aluminum is preferable in terms of availability, cost and stability of metal chelate.

The thickness of the gate insulating layer is preferably 0.05 to 5 μm, more preferably 0.1 to 1 μm. By setting the film thickness within this range, uniform thin film formation becomes easy. The film thickness can be measured by an atomic force microscope, ellipsometry or the like.

Although the method for producing the gate insulating layer is not particularly limited, for example, a method of subjecting a coating film obtained by applying a composition containing a material for forming the insulating layer to a substrate and drying, if necessary, heat treatment It can be mentioned. Examples of the coating method include known coating methods such as a spin coating method, a blade coating method, a slit die coating method, a screen printing method, a bar coater method, a mold method, a printing transfer method, an immersion pulling method, and an inkjet method. The heat treatment temperature of the coating film is preferably in the range of 100 to 300 ° C.

The gate insulating layer may be a single layer or a plurality of layers. Further, one layer may be formed of a plurality of insulating materials, or a plurality of insulating materials may be stacked to form a plurality of insulating layers.

(Nano carbon)
The nanocarbon is a substance made of carbon and having a structure of nanometer size, and examples thereof include fullerene, carbon nanotube (CNT), graphene, carbon nanohorn, graphene nanoribbon, incorporated CNT, contained fullerene and the like. From the viewpoint of semiconductor properties, as nanocarbons, fullerenes, CNTs, and graphenes are preferable, and CNTs are more preferable.

(CNT)
As the CNT, a single layer CNT in which one carbon film (graphene sheet) is cylindrically wound, a two-layer CNT in which two graphene sheets are concentrically wound, and a plurality of graphene sheets are concentric Any of multi-walled CNT wound around may be used. In order to obtain high semiconductor characteristics, it is preferable to use single-walled CNTs. The CNTs can be obtained by an arc discharge method, CVD, a laser ablation method or the like.

In addition, it is more preferable that the total content of the CNTs is 100% by weight and that the CNTs contain 80% by weight or more of semiconducting CNTs. More preferably, it contains 90% by weight or more of semiconducting CNT, and particularly preferably contains 95% by weight or more of semiconducting CNT. A known method can be used as a method of including 80 wt% or more of semiconducting CNTs in CNTs. For example, a method of ultracentrifugation in the presence of a density gradient agent, a method of selectively attaching a specific compound to the surface of a semiconducting or metallic CNT, and separating using a difference in solubility, a difference in electrical properties And separation methods by electrophoresis and the like. As a method of measuring the content of the semiconducting CNT in the CNT, a method of calculating from the absorption area ratio of the visible-near infrared absorption spectrum, a method of calculating from the intensity ratio of the Raman spectrum, and the like can be mentioned.

In the present invention, when CNTs are used in the semiconductor layer of the semiconductor element, the length of the CNTs is preferably shorter than the distance between the source electrode and the drain electrode (hereinafter, “inter-electrode distance”). The average length of the CNT depends on the distance between the electrodes, but is preferably 2 μm or less, more preferably 1 μm or less. Examples of methods for shortening the length of CNTs include acid treatment and freeze grinding.

The average length of the CNTs is determined as the average of the lengths of 20 randomly picked CNTs. As a method of measuring the average CNT length, 20 CNTs are randomly picked up from images obtained by an atomic force microscope, a scanning electron microscope, a transmission electron microscope or the like, and the average value of their lengths is obtained. How to get

Generally commercially available CNTs have a distribution in length, and may contain CNTs longer than the distance between electrodes. Therefore, it is preferable to add a step of making the CNTs shorter than the inter-electrode distance. For example, a method of cutting CNTs into a short fiber shape by acid treatment with nitric acid, sulfuric acid or the like, ultrasonication, or freeze grinding is effective. Moreover, it is more preferable to use the separation by a filter in combination in that the purity of the CNT is improved.

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

In the present invention, it is preferable to provide a step of uniformly dispersing CNTs in a solvent and filtering the dispersion with a filter. By obtaining CNTs smaller than the filter pore size from the filtrate, CNTs shorter than the inter-electrode distance can be efficiently obtained. In this case, a membrane filter is preferably used as the filter. The pore diameter of the filter used for filtration may be smaller than the distance between electrodes, and is preferably 0.5 to 10 μm.

(Carbon nanotube composite)
In the CNT used in the present invention, it is preferable to use a conjugated polymer attached to at least a part of the surface of the CNT (hereinafter, the CNT to which the conjugated polymer is attached is referred to as “CNT composite”). Here, a conjugated polymer refers to a compound in which the repeating unit has a conjugated structure and the degree of polymerization is 2 or more.

By attaching the conjugated polymer to at least a part of the surface of the CNT, it becomes possible to uniformly disperse the CNT in the solution without losing the high electrical properties of the CNT. If a solution in which CNTs are uniformly dispersed is used, it becomes possible to form a film containing uniformly dispersed CNTs by the coating method. Thereby, high semiconductor characteristics can be realized.

The state in which the conjugated polymer is attached to at least a part of the surface of the CNT means the state in which the conjugated polymer covers a part or all of the surface of the CNT. The reason that the conjugated polymer can coat the CNTs is presumed to be due to the interaction caused by the overlapping of the π electron clouds derived from the conjugated structure of the two.

Whether or not CNTs are coated with a conjugated polymer can be determined from the reflected color. The reflected color of the coated CNT is close to the reflected color of the conjugated polymer unlike the reflected color of the uncoated CNT. Quantitatively, the presence of deposits on the CNTs can be confirmed by elemental analysis such as X-ray photoelectron spectroscopy (XPS), and the weight ratio between the CNTs and the deposits can be measured.

In addition, the weight average molecular weight of the conjugated polymer is preferably 1000 or more in view of the ease of adhesion to CNTs.

As a method of attaching the conjugated polymer to the CNT, (I) a method of adding and mixing the CNT into the melted conjugated polymer, (II) the conjugated polymer is dissolved in a solvent, Method of adding and mixing CNTs, (III) Method of pre-dispersing CNTs in a solvent by ultrasonic wave etc., adding and mixing conjugated polymer there, (IV) conjugated polymer in solvent And CNT, and the method of irradiating and mixing an ultrasonic wave to this mixed system, etc. are mentioned. In the present invention, any method may be used, and a plurality of methods may be combined.

Examples of conjugated polymers include polythiophene polymers, polypyrrole polymers, polyaniline polymers, polyacetylene polymers, poly-p-phenylene polymers and poly-p-phenylene vinylene polymers. There is no particular limitation. As the above-mentioned polymers, those in which single monomer units are arranged are preferably used, but those obtained by block copolymerizing different monomer units, those obtained by random copolymerization, and those obtained by graft polymerization are also preferably used.

Among the above polymers, in the present invention, a polythiophene-based polymer is preferably used from the viewpoint of easy adhesion to CNTs and easy formation of a CNT complex. Among the polythiophene polymers, those containing a fused heteroaryl unit having a nitrogen-containing double bond in the ring and a thiophene unit in a repeating unit are more preferable.

As a fused heteroaryl unit having a nitrogen-containing double bond in the ring, thienopyrrole, pyrrolothiazole, pyrrolopyridazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, benzothiadiazole, quinoline, quinoxaline, benzotriazine, thieno oxazole And units such as thienopyridine, thienothiazine, thienopyrazine and the like. Among these, benzothiadiazole unit or quinoxaline unit is particularly preferable. By having these units, the adhesion between the CNTs and the conjugated polymer is enhanced, and the CNTs can be dispersed more favorably in the semiconductor layer.

Furthermore, as the above-mentioned conjugated polymer, one having a structure represented by the following general formula (11) is particularly preferable.

Here, R ¹⁹ to R ^{24, which} may be the same or different, each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, Arylether group, arylthioether group, aryl group, heteroaryl group, halogen atom, cyano group, formyl group, carbamoyl group, amino group, alkylcarbonyl group, arylcarbonyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, It represents an alkylcarbonyloxy group, an arylcarbonyloxy group or a silyl group. Further, in R ¹⁹ to R ²⁴ , adjacent groups may form a ring structure. A is selected from a single bond, an arylene group, a heteroarylene group other than a thienylene group, an ethenylene group and an ethynylene group. l and m each represent an integer of 0 to 10, and l + m ≧ 1. n represents a range of 2 to 1000. When l, m and n are 2 or more, in each repeating unit, R ¹⁹ to R ²⁴ and A may be the same or different.

The alkyl group indicates, for example, a saturated aliphatic hydrocarbon group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like. The alkyl group may or may not have a substituent. When the alkyl group has a substituent, the substituent is not particularly limited, and examples thereof include an alkoxy group, an aryl group and a heteroaryl group. The substituent may further have a substituent. Unless otherwise stated, descriptions on these substituents are also common to the following description. The carbon number of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 8 or less from the viewpoint of availability and cost.

The cycloalkyl group is, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl group, cyclohexyl group, norbornyl group, adamantyl group and the like. The cycloalkyl group may or may not have a substituent. The carbon number of the cycloalkyl group is not particularly limited, but a range of 3 or more and 20 or less is preferable.

The heterocyclic group refers to, for example, a group derived from an aliphatic ring having an atom other than carbon in the ring, such as a pyran ring, a piperidine ring, and an amido ring. The heterocyclic group may or may not have a substituent. The carbon number of the heterocyclic group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The alkenyl group means, for example, an unsaturated aliphatic hydrocarbon group containing a double bond, such as a vinyl group, an aryl group and a butadienyl group. The alkenyl group may or may not have a substituent. The carbon number of the alkenyl group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The cycloalkenyl group means, for example, an unsaturated alicyclic hydrocarbon group containing a double bond, such as cyclopentenyl group, cyclopentadienyl group, cyclohexenyl group and the like. The cycloalkenyl group may or may not have a substituent. The carbon number of the cycloalkenyl group is not particularly limited, but a range of 3 or more and 20 or less is preferable.

The alkynyl group means an unsaturated aliphatic hydrocarbon group containing a triple bond, such as an ethynyl group. The alkynyl group may or may not have a substituent. The number of carbon atoms in the alkynyl group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The alkoxy group refers to, for example, a functional group in which one of the ether bonds is substituted with an aliphatic hydrocarbon group, such as a methoxy group, an ethoxy group, and a propoxy group. The alkoxy group may or may not have a substituent. The carbon number of the alkoxy group is not particularly limited, but a range of 1 or more and 20 or less is preferable.

The alkylthio group is one in which the oxygen atom of the ether bond of the alkoxy group is substituted by a sulfur atom. The alkylthio group may or may not have a substituent. The carbon number of the alkylthio group is not particularly limited, but a range of 1 or more and 20 or less is preferable.

The aryl ether group refers to, for example, a functional group such as a phenoxy group or a naphthoxy group in which one of the ether bonds is substituted with an aromatic hydrocarbon group. The aryl ether group may or may not have a substituent. The carbon number of the aryl ether group is not particularly limited, but a range of 6 or more and 40 or less is preferable.

The arylthioether group is one in which the oxygen atom of the ether bond of the arylether group is substituted by a sulfur atom. The aryl thioether group may or may not have a substituent. The carbon number of the arylthioether group is not particularly limited, but a range of 6 or more and 40 or less is preferable.

The aryl group is, for example, an aromatic hydrocarbon group such as phenyl group, naphthyl group, biphenyl group, anthracenyl group, phenanthryl group, terphenyl group, pyrenyl group and the like. The aryl group may or may not have a substituent. The carbon number of the aryl group is not particularly limited, but a range of 6 or more and 40 or less is preferable.

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

The halogen atom represents fluorine, chlorine, bromine or iodine.

The alkylcarbonyl group refers to, for example, a functional group such as an acetyl group or a hexanoyl group in which one of the carbonyl bonds is substituted with an aliphatic hydrocarbon group. The alkylcarbonyl group may or may not have a substituent. The carbon number of the alkylcarbonyl group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The arylcarbonyl group refers to, for example, a functional group such as a benzoyl group in which one of the carbonyl bonds is substituted with an aromatic hydrocarbon group. The arylcarbonyl group may or may not have a substituent. The carbon number of the arylcarbonyl group is not particularly limited, but a range of 7 or more and 40 or less is preferable.

The alkoxycarbonyl group indicates, for example, a functional group such as a methoxycarbonyl group in which one of the carbonyl bonds is substituted with an alkoxy group. The alkoxycarbonyl group may or may not have a substituent. The carbon number of the alkoxycarbonyl group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The aryloxycarbonyl group refers to, for example, a functional group in which one of the carbonyl bonds is substituted with an aryloxy group, such as a phenoxycarbonyl group. The aryloxy carbonyl group may or may not have a substituent. The carbon number of the aryloxycarbonyl group is not particularly limited, but a range of 7 or more and 40 or less is preferable.

The alkylcarbonyloxy group indicates a functional group in which one of ether linkages is substituted with an alkylcarbonyl group, such as an acetoxy group, for example. The alkylcarbonyloxy group may or may not have a substituent. The carbon number of the alkylcarbonyloxy group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

The arylcarbonyloxy group indicates a functional group in which one of ether linkages is substituted with an arylcarbonyl group, such as a benzoyloxy group. The arylcarbonyloxy group may or may not have a substituent. The carbon number of the arylcarbonyloxy group is not particularly limited, but a range of 7 or more and 40 or less is preferable.

The carbamoyl group, the amino group and the silyl group may or may not have a substituent.

The case where adjacent groups combine with each other to form a ring structure is, for example, when R ¹⁹ and R ²⁰ are bonded to each other to form a conjugated or non-conjugated ring structure, as described in the above general formula (11). It is a case to form. As a constituent element of the ring structure, each atom of nitrogen, oxygen, sulfur, phosphorus and silicon may be contained in addition to carbon atoms. In addition, the ring structure may be a structure fused to another ring.

Next, A in the general formula (11) will be described. The arylene group is a divalent (two bonding sites) aromatic hydrocarbon group, which may be unsubstituted or substituted. Examples of the substituent when substituted include the above-mentioned alkyl group, heteroaryl group and halogen. Preferred examples of the arylene group include phenylene group, naphthylene group, biphenylene group, phenanthrylene group, anthrylene group, terphenylene group, pyrenylene group, fluorenylene group, perylenylene group and the like.

The heteroarylene group is a divalent heteroaromatic ring group and may be unsubstituted or substituted. Preferred specific examples of the heteroarylene group include pyridinene group, pyrazylene group, quinolinylene group, isoquinolylene group, quinoxalylene group, acridinylene group, indolylene group, carbazolylene group, etc. And bivalent groups derived from heteroaromatic rings such as thiophene, benzosilole and dibenzosilole.

L and m in the general formula (11) represent integers of 0 to 10, and l + m ≧ 1. By containing a thiophene unit in the structure of the general formula (11), the adhesion between the conjugated polymer and the CNT is improved, and the dispersibility of the CNT is improved. Preferably, l and m are each 1 or more, more preferably l + m ≧ 4. In addition, l + m ≦ 12 is preferable from the viewpoint of the synthesis of the monomer and the ease of polymerization thereafter.

N represents the degree of polymerization of the conjugated polymer and is in the range of 2 to 1,000. N is preferably in the range of 3 to 500, in consideration of the ease of adhesion to CNTs. In the present invention, the degree of polymerization n is a value determined from the weight average molecular weight. The weight average molecular weight is measured using GPC (gel permeation chromatography), and calculated using a polystyrene standard sample.

Moreover, it is preferable that the conjugated polymer is soluble in a solvent in view of the easiness of formation of the CNT complex. In the general formula (11), at least one of R ¹⁹ to R ²⁴ is preferably an alkyl group.

As a conjugated polymer, those having the following structure can be mentioned.

The conjugated polymer can be synthesized by a known method. For example, as a method of connecting thiophenes, a method of coupling a halogenated thiophene and a thiophene boronic acid or a thiophene boronic acid ester under a palladium catalyst, a halogenated thiophene and a thiophene Grignard reagent under a nickel or palladium catalyst And coupling methods. Moreover, also when connecting another unit and a thiophene unit, the halogenated other unit and a thiophene unit can be coupled by the same method. Also, a conjugated polymer can be obtained by introducing a polymerizable functional group at the terminal of the monomer thus obtained and advancing the polymerization under a palladium catalyst or a nickel catalyst.

As the conjugated polymer, it is preferable to use one from which impurities such as raw materials and by-products used in the synthesis process have been removed. As a method of removing the impurities, for example, silica gel column chromatography method, Soxhlet extraction method, filtration method, ion exchange method, chelate method and the like can be used. Two or more of these methods may be combined.

(Semiconductor layer)
The semiconductor layer contains nanocarbon. At this time, the nanocarbon is preferably fullerene, CNT or graphene, more preferably CNT. Furthermore, it is preferable to attach a conjugated polymer and use CNT as a CNT composite. The semiconductor layer may further contain an organic semiconductor or an insulating material as long as the electric characteristics are not impaired.

The thickness of the semiconductor layer is preferably 1 nm or more and 100 nm or less. Within this range, uniform thin film formation is facilitated. The thickness of the semiconductor layer is more preferably 1 nm or more and 50 nm or less, and still more preferably 1 nm or more and 20 nm or less. The film thickness can be measured by an atomic force microscope, ellipsometry or the like.

As a method of forming the semiconductor layer, it is possible to use a dry method such as resistance heating evaporation, electron beam, sputtering, or CVD, but from the viewpoint of manufacturing cost and compatibility with a large area, use a coating method. Is preferred. Specifically, a spin coating method, a blade coating method, a slit die coating method, a screen printing method, a bar coater method, a mold method, a printing transfer method, an immersion pulling method, an inkjet method and the like can be preferably used. Among these, it is preferable to select the coating method according to the coating film characteristics to be obtained, such as coating film thickness control and orientation control. In addition, the formed coating may be subjected to an annealing treatment under the atmosphere, under reduced pressure, or under an inert gas atmosphere such as nitrogen or argon.

(Second insulating layer)
The second insulating layer is formed on the semiconductor layer opposite to the side on which the gate insulating layer is formed. The side opposite to the side on which the gate insulating layer is formed with respect to the semiconductor layer refers to, for example, the upper side of the semiconductor layer when the gate insulating layer is provided below the semiconductor layer. By forming the second insulating layer, the semiconductor layer can be protected.

The second insulating layer contains a polymer having a structure represented by the general formula (1) in at least a part of a side chain. The amino group in the polymer can convert a CNT-FET, which usually exhibits p-type semiconductor characteristics, into a semiconductor element which exhibits n-type semiconductor characteristics. Furthermore, it is presumed that the stability of the n-type TFT characteristics is improved by fixing the amino group as the side chain of the polymer.

As a main chain skeleton of the polymer which has a structure represented by General formula (1) in at least a part of side chain, polyolefin, polyester, polyamide, polyimide, polyurethane, siloxane, etc. are mentioned, for example.

In the general formula (1), R ¹ and R ² are each independently composed of one or more atoms selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom Group is shown. R ³ and R ⁴ each independently represent a hydrogen atom or a group represented by the following general formula (2).

As R ¹ to R ⁷ , for example, a structure comprising an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a heteroaryl group, or a combination thereof, or an amide group with these, an ester group, an ether group, a urea group, an imide Although the structure etc. which consist of a combination with 1 or more types selected from the group which consists of groups are mentioned, it is not restricted to this.

The arylene group, the heteroarylene group, the alkyl group, the alkoxy group, the cycloalkyl group, the aryl group and the heteroaryl group are as described above in the section (Carbon nanotube composite).

The amino group in the general formula (1) is a group in which the atom bonded to the nitrogen atom is a hydrogen atom or a carbon atom. However, any atom further bonded to the carbon atom is bonded to the carbon atom via a single bond. Specific examples of such an amino group include, for example, a methylamino group, a dimethylamino group, and a dicyclohexylamino group, but not limited thereto. In addition, the amino group may or may not be further contained in R ¹ to R ⁷ .

The polymer having the structure represented by the general formula (1) in at least a part of the side chain has a ratio of the number of nitrogen atoms constituting the amino group in the polymer to the total number of atoms of the polymer (amino group in the polymer It is preferable that the number of nitrogen atoms to constitute / the total number of atoms of the polymer) is 1/10000 to 1/10. By being in this range, it is presumed that the amino group works effectively and the conversion to the n-type semiconductor device can be effectively realized. When an amino group is further contained in the main chain skeleton or R ¹ to R ⁷ , the nitrogen atom is also included in the number of nitrogen atoms constituting the amino group.

The ratio of the number of nitrogen atoms constituting the amino group in the polymer to the total number of atoms of the polymer can be calculated by determining the composition formula and the nitrogen atom weight corresponding to the amino group by elemental analysis such as XPS.

From the viewpoint of availability and cost, it is preferable that the polymer having at least a part of the side chain a structure represented by General Formula (1) is a polymer having a unit structure represented by General Formula (3) .

In the general formula (3), R ¹ to R ⁴ are as described above. R ⁸ represents a single bond or a divalent group constituted by one or more types of atoms selected from carbon atom, oxygen atom, nitrogen atom, silicon atom, phosphorus atom and sulfur atom. R ⁹ represents a group constituted by one or more types of atoms selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom.

As R ⁸ , for example, a structure comprising an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, a heteroarylene group, or a combination thereof, or an amide group with these, an ester group, an ether group, a urea group or an imide group Although the structure etc. which consist of a combination with 1 or more types selected from is included, it is not restricted to this.

As R ⁹ , for example, a structure comprising an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a heteroaryl group or a combination thereof or an amide group, an ester group, an ether group, a urea group or an imide group Although the structure etc. which consist of a combination with 1 or more types chosen from a group are mentioned, it is not restricted to this.

Among these groups, an alkylene group is, for example, a divalent saturated aliphatic group such as methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, sec-butylene group, tert-butylene group, etc. Indicates a hydrocarbon group. The alkylene group may or may not further have a substituent. The carbon number of the alkylene group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 8 or less from the viewpoint of availability and cost.

The oxyalkylene group indicates, for example, a divalent functional group in which an aliphatic hydrocarbon group is bonded via an ether bond such as an oxyethylene group or an oxypropylene group, and the aliphatic hydrocarbon group further has a substituent. It may or may not have. The carbon number of the oxyalkoxy group is not particularly limited, but a range of 1 or more and 20 or less is preferable.

The cycloalkylene group is, for example, a divalent saturated alicyclic hydrocarbon group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group or the like, which may have a substituent. You do not need to have it. The carbon number of the cycloalkylene group is not particularly limited, but a range of 2 or more and 20 or less is preferable.

As a unit structure represented by General formula (3), for example, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, 2- (diisopropylamino) ethyl acrylate, Examples thereof include acrylic monomers such as 2- (dimethylamino) isopropyl acrylate and a repeating unit structure of an acrylic resin using a monomer obtained by replacing such acrylate with methacrylate. The repeating unit structure may be used alone or in combination of two or more.

Examples of the polymer having a unit structure represented by the general formula (3) include polyallylamine and poly (dimethylallylamine).

It is more preferable that the polymer which has a structure represented by the said General formula (1) in a part of side chain at least has a unit structure further represented by General formula (4). Due to the presence of a polar group such as Y, it is presumed that the amino group works effectively and the conversion to an n-type semiconductor device can be effectively realized.

In the general formula (4), Y represents an amide group, an ester group, a urea group, a carbonyl group, an imide group, a ureido group, a thioamide group, a thioester group, a thiourea group, a thiocarbonyl group, a thioimide group and a thioureido group Indicates the selected group. R ¹⁰ represents a group constituted by one or more kinds of atoms selected from a hydrogen atom, a carbon atom, an oxygen atom, a silicon atom, a phosphorus atom and a sulfur atom. R ¹¹ represents a single bond or a divalent group constituted by one or more kinds of atoms selected from a hydrogen atom, a carbon atom, an oxygen atom, a silicon atom, a phosphorus atom and a sulfur atom. R ¹² represents a group constituted by one or more types of atoms selected from carbon atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom.

R ¹⁰ represents, for example, a structure consisting of an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a heteroaryl group, or a combination thereof or one or more selected from the group consisting of an ester group and an ether group Although the structure etc. which consist of a combination etc. are mentioned, it is not restricted to this.

R ¹¹ is, for example, one or more selected from the group consisting of an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, a heteroarylene group, or a combination thereof or an ester group and an ether group Although the structure etc. which consist of combinations of is mentioned, it is not restricted to this.

As R ¹² , for example, a structure consisting of an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a heteroaryl group, or a combination thereof or one or more selected from the group consisting of an ester group and an ether group Although the structure etc. which consist of a combination etc. are mentioned, it is not restricted to this.

Examples of the unit structure represented by the general formula (4) include methyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, i-propane acrylate, N-methoxymethyl acrylamide, N- Ethoxymethyl acrylamide, Nn-butoxymethyl acrylamide, N-isobutoxy methyl acrylamide, butoxy triethylene glycol acrylate, dicyclopentanyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl Acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy ethylene glycol acrylate, methoxy di Acrylic monomers such as thylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, and the like Repeating unit structure of an acrylic resin using, as a monomer, one obtained by replacing acrylate with methacrylate; repeating unit structure of polyvinylpyrrolidone; the above-mentioned ester group is urea group, carbonyl group, imide group, ureido group, thioamide group, thioester group, thiourea group , A thiocarbonyl group, a thioimide group, a repeating unit structure substituted with a thioureido group, and the like. The repeating unit structure may be used alone or in combination of two or more. In addition, one or more Y may be contained in the repeating unit structure.

The polymer having a unit structure represented by the general formulas (3) and (4) has a ratio of the unit structure represented by the general formula (4) to the unit structure represented by the general formula (3) It is preferable that the number of moles of the unit structure represented by 4) / the number of moles of the unit structure represented by the general formula (3) is 90/10 to 10/90. By being in this range, it is presumed that the amino group works effectively and the conversion to the n-type semiconductor device can be effectively realized. The ratio is more preferably 90/10 to 30/70, still more preferably 90/10 to 40/60. The ratio of the unit structure represented by the general formula (4) to the unit structure represented by the general formula (3) can be calculated by evaluating the ratio of the amino group or Y by XPS.

The thickness of the second insulating layer is preferably 500 nm or more, more preferably 1.0 μm or more, still more preferably 3.0 μm or more, and particularly preferably 10 μm or more. By setting the film thickness within this range, conversion to a semiconductor element exhibiting higher n-type semiconductor characteristics can be achieved, and the stability of n-type TFT characteristics is improved. The upper limit is not particularly limited, but is preferably 500 μm or less.

The film thickness of the second insulating layer was randomly selected from among the portions of the second insulating layer located on the semiconductor layer in the image obtained by measuring the cross section of the second insulating layer with a scanning electron microscope The film thickness at 10 locations is calculated and taken as the value of the arithmetic mean.

The second insulating layer preferably further contains an electron donating compound having one or more atoms selected from a nitrogen atom and a phosphorus atom. Electron donating ability refers to the ability of one compound to donate an electron to another compound. The electron donating compound is a compound having an electron donating ability. By including such an electron donating compound in the second insulating layer, it can be converted to a semiconductor element having higher n-type semiconductor characteristics.

As an electron donor, an amine compound, an imine type compound, an aniline type compound, a nitrile type compound, an alkyl phosphine type compound etc. can be mentioned, for example.

Examples of amine compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, diisopropylethylamine, cyclohexylamine, methylcyclohexylamine, dimethylcyclohexylamine, dicyclohexylamine, dicyclohexylmethylamine, tricyclohexylamine, cyclooctylamine and cyclooctylamine. Decylamine, cyclododecylamine, 1-azabicyclo [2.2.2] octane (quinuclidine), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4 .3.0] Non-5-ene (DBN), 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1,5,7-tria Xabicyclo 4.4.0] dec-5-ene (MTBD), poly (melamine -co- formaldehyde), tetramethylethylenediamine, diphenylamine, triphenylamine, phenylalanine, N, etc. N- dimethyl-4-aminopyridine.

Examples of imine compounds include ethyleneimine, N-methylhexane-1-imine, N-methyl-1-butyl-1-hexaneimine, propane-2-imine, methanediimine, N-methylethaneimine, ethane-1,2 -Diimine etc. are mentioned.

Aniline, toluidine etc. are mentioned as an aniline type compound.

Examples of nitrile compounds include acetonitrile and acrylonitrile. Other compounds include allantoin, 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, dicyandiamidine, citrulline, piperidine, imidazole, pyrimidine, julolidine and the like.

Examples of alkyl phosphine compounds include tributyl phosphine, tri-tert-butyl phosphine, triphenyl phosphine and the like.

Among these, from the viewpoint of expression of higher n-type semiconductor characteristics, the electron donating compound is preferably a compound having a nitrogen atom, and more preferably a compound having a ring structure containing a nitrogen atom. . Examples of the compound having a ring structure containing a nitrogen atom include polyvinyl pyrrolidone, N-methyl pyrrolidone, polyvinyl polypyrrolidone, β-lactam, γ-lactam, δ-lactam, ε-caprolactam, polyimide, phthalimide, maleimide, maleimide, alloxane, succinimide Uracil, thymine, 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, quinuclidine, DBU, DBN, TBD, MTBD, piperidine, imidazole, pyrimidine, julolidine and the like.

Further, it is particularly preferable that the electron donor compound is any one or more compounds selected from an amidine compound and a guanidine compound. Examples of amidine compounds include DBU and DBN. Examples of guanidine compounds include TBD and MTBD. These compounds are preferable because they have particularly high electron donating properties, and thus the performance of the CNT using FET as an n-type semiconductor device is further improved.

The second insulating layer may be a single layer or a plurality of layers, one layer may be formed of a plurality of insulating materials, or a plurality of insulating materials may be stacked.

The method of forming the second insulating layer is not particularly limited, and dry methods such as resistance heating evaporation, electron beam, sputtering, and CVD may be used, but from the viewpoint of manufacturing cost and adaptation to a large area. It is preferable to use a coating method. The application method at least includes the steps of applying and drying a composition containing a polymer and a solvent contained in the second insulating layer.

Specifically, spin coating method, blade coating method, slit die coating method, screen printing method, bar coater method, mold method, printing transfer method, immersion pulling method, ink jet method, drop casting method etc. are preferable as the coating method. It can be used. Among these, it is preferable to select the coating method according to the coating film characteristics to be obtained, such as coating film thickness control and orientation control.

The solvent for dissolving the polymer contained in the second insulating layer when forming the second insulating layer using a coating method is not particularly limited, but an organic solvent is preferable. Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, ethylene glycol dimethyl ether, Ethers such as ethylene glycol diethyl ether, ethylene glycol dibutyl ether and diethylene glycol ethyl methyl ether; ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl -3-Methoxybutyl acetate Esters such as methyl lactate, ethyl lactate and butyl lactate; acetones such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, cyclopentanone and 2-heptanone; butyl alcohol, isobutyl alcohol, pentanol, Alcohols such as 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol; Aromatic hydrocarbons such as toluene and xylene; Hexane, decahydronaphthalene And the like.

Two or more of these may be used as the solvent. Among them, it is preferable to contain a solvent having a boiling point of 110 to 200 ° C. at 1 atm. When the boiling point of the solvent is 110 ° C. or more, volatilization of the solvent is suppressed at the time of solution application, and the coatability becomes good. When the boiling point of the solvent is 200 ° C. or less, the amount of the solvent remaining in the insulating film is reduced, and the second insulating layer having better heat resistance and chemical resistance can be obtained.

In addition, the formed coating may be subjected to annealing treatment or hot-air drying in the atmosphere, under reduced pressure, or in an inert gas atmosphere such as nitrogen or argon. Specifically, for example, the annealing conditions include 50 to 150 ° C., 3 to 30 minutes, and under a nitrogen atmosphere. Such a drying step allows firm drying if the coating is not sufficiently dried.

(Barrier layer)
The n-type semiconductor device according to the embodiment of the present invention preferably includes a layer (barrier layer) having a water vapor transmission rate of 20 g / (m ² · 24 h) or less on the second insulating layer. The water vapor transmission rate of the barrier layer is more preferably 10 g / (m ² · 24 h) or less, still more preferably 1 g / (m ² · 24 h) or less. By being in this range, stable n-type semiconductor characteristics can be realized without being affected by moisture in the air.

FIG. 3 is a schematic cross-sectional view showing a third example of the semiconductor device according to the embodiment of the present invention. A gate electrode 2 formed on an insulating base material 1, a gate insulating layer 3 covering it, a source electrode 5 and a drain electrode 6 provided thereon, and a semiconductor layer provided between the electrodes 4, a second insulating layer 8 covering the semiconductor layer, and a barrier layer 9 covering the second insulating layer. The semiconductor layer 4 contains nanocarbon 7.

FIG. 4 is a schematic cross-sectional view showing a fourth example of the semiconductor device according to the embodiment of the present invention. A gate electrode 2 formed on an insulating substrate 1, a gate insulating layer 3 covering it, a semiconductor layer 4 provided thereon, and a source electrode 5 and a drain electrode 6 formed thereon , And a second insulating layer 8 provided thereon, and a barrier layer 9 covering the second insulating layer. The semiconductor layer 4 contains nanocarbon 7.

From the viewpoint of the performance stability of the n-type semiconductor device, the barrier layer preferably contains one or more selected from fluorine resins, chlorine resins, nitrile resins, polyesters, and polyolefins. In addition to the low water vapor permeability of these polymers, film formation by drying under mild annealing conditions is possible in the process of forming a barrier layer by a coating method, and the characteristic deterioration of n-type semiconductor devices due to annealing is suppressed. It is because it can.

The fluorine-based resin is a polymer containing a fluorine atom, and examples thereof include polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, and copolymers of vinylidene fluoride and trifluorinated ethylene. Be

The chlorine-based resin is a polymer containing a chlorine atom, and examples thereof include polyvinyl chloride, polyvinylidene chloride, a vinyl chloride-vinyl acetate copolymer and the like.

The nitrile resin is a polymer containing a nitrile group, and examples thereof include polyacrylonitrile, polyallyl cyanide and the like.

As polyester, a polyethylene terephthalate etc. are mentioned, for example.

Examples of the polyolefin include polyethylene, polypropylene, polybutadiene, polystyrene, cycloolefin polymer and the like.

From the viewpoint of water vapor permeation, fluorine resins, chlorine resins and polyolefin resins are more preferable. Among them, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene chloride and cycloolefin polymers are preferable.

The film thickness of the barrier layer is preferably 1.0 μm or more, more preferably 3.0 μm or more, and particularly preferably 10 μm or more. By setting the film thickness in this range, it is possible to enhance the water vapor shielding property by the barrier layer. The upper limit is not particularly limited, but is preferably 500 μm or less.

The film thickness of the barrier layer is obtained by measuring the cross section of the barrier layer with a scanning electron microscope, and of the obtained image, 10 films randomly selected from the second insulating layer portion located on the semiconductor layer The thickness is calculated and taken as the value of its arithmetic mean.

The method for forming the barrier layer is not particularly limited, and methods such as resistance heating evaporation, electron beam, lamination, sputtering, and CVD can be used, but application is performed from the viewpoint of manufacturing cost and adaptation to a large area. It is preferred to use the method. The application method at least includes the steps of applying and drying a composition containing the polymer contained in the barrier layer and a solvent. In addition, the barrier layer may be formed as a semiconductor element by resistance heating vapor deposition, electron beam beam, lamination, sputtering, CVD, a coating method, or the like on a wireless communication device and a product tag described later.

In the semiconductor device according to the embodiment of the present invention, the current (the current between the source and the drain) flowing between the source electrode and the drain electrode can be controlled by changing the gate voltage. Then, the mobility μ (cm ² / V · s) of the semiconductor element can be calculated using the following equation (a).

μ = (δId / δVg) L · D / (W · εr · ε · Vsd) (a)
Where Id is source-drain current (A), Vsd is source-drain voltage (V), Vg is gate voltage (V), D is thickness of gate insulating layer (m), L is channel length (m), W is the channel width (m), ε r is the dielectric constant of the gate insulating layer (F / m), ε is the vacuum dielectric constant (8.85 × 10 ^-12 F / m), and δ is the change in the corresponding physical quantity Indicates

Also, the threshold voltage can be obtained from the intersection of the extension of the linear portion in the Id-Vg graph and the Vg axis.

The n-type semiconductor element operates by conducting a source-drain path by applying a positive voltage higher than a threshold voltage to the gate electrode. A high-performance n-type semiconductor device with good characteristics is one having a small absolute value of threshold voltage and a high mobility.

(Method of manufacturing semiconductor device)
The method for producing a semiconductor device according to the embodiment of the present invention is not particularly limited, but it is preferable to include the step of applying and drying a composition containing the polymer and a solvent to form the second insulating layer. . Moreover, it is preferable to include the process of forming a semiconductor layer by the apply | coating method. Forming the semiconductor layer by a coating method includes at least a step of applying a solution in which a material for forming the semiconductor layer is dissolved, and a step of drying the coating film.

Hereinafter, a method of manufacturing a semiconductor device according to the embodiment of the present invention will be specifically described by taking a case of manufacturing a semiconductor device having a structure shown in FIG. 3 as an example.

First, as shown in FIG. 5A, the gate electrode 2 is formed on the insulating substrate 1 by the method described above.

Next, as shown in FIG. 5B, a solution containing an organic compound containing a bond of a silicon atom and a carbon atom is applied and dried to form the gate insulating layer 3.

Next, as shown in FIG. 5C, the source electrode 5 and the drain electrode 6 are simultaneously formed on the top of the gate insulating layer 3 using the same material by the above-described method.

Next, as shown in FIG. 5D, the semiconductor layer 4 is formed between the source electrode 5 and the drain electrode 6 by the method described above.

Next, as shown in FIG. 5 (e), a second insulating layer is formed by the method described above so as to cover the semiconductor layer 4, and then, as shown in FIG. 5 (f), the second insulating layer is formed. A barrier layer is formed as described above to cover it. By thus forming the second insulating layer and the barrier layer, an n-type semiconductor device having a barrier layer can be manufactured.

<Wireless communication device>
Next, a wireless communication apparatus according to an embodiment of the present invention, which has the n-type semiconductor element, will be described. The wireless communication apparatus is an apparatus that performs electric communication by receiving a carrier wave transmitted from an antenna mounted on a reader / writer, such as an RFID tag, and transmitting a signal.

Specifically, for example, the antenna of the RFID tag receives a radio signal transmitted from an antenna mounted on the reader / writer. Then, an alternating current generated in response to the signal is converted into a direct current by the rectifier circuit, and the RFID tag generates electricity. Next, the generated RFID tag receives a command from the wireless signal and performs an operation according to the command. After that, the response of the result according to the command is transmitted as a wireless signal from the antenna of the RFID tag to the antenna of the reader / writer. The operation according to the command is performed at least by a known demodulation circuit, operation control logic circuit, and modulation circuit.

A wireless communication apparatus according to an embodiment of the present invention at least includes the above-described semiconductor element or complementary semiconductor device, and an antenna. As a more specific configuration of the wireless communication apparatus according to the embodiment of the present invention, for example, one shown in FIG. 6 can be mentioned. This is sent from a power generation unit that rectifies the modulation wave signal from the outside received by the antenna 50 and supplies power to each part, a demodulation circuit that demodulates the modulation wave signal and sends it to the control circuit, and a control circuit The modulation circuit that modulates the received data and sends it to the antenna, the control circuit that writes the data demodulated by the demodulation circuit to the storage circuit, and reads the data from the storage circuit and sends it to the modulation circuit. Each circuit unit is electrically connected. The demodulation circuit, the control circuit, the modulation circuit, and the storage circuit are formed of the above-described n-type semiconductor element or complementary semiconductor device, and may further include a capacitor, a resistance element, and a diode. The memory circuit further includes a non-volatile rewritable memory unit such as an EEPROM (Electrically Erasable Programmable Read-Only Memory), an FeRAM (Ferroelectric Random Access Memory), or the like. The power supply generation unit is composed of a capacitor and a diode.

The antenna, the capacitor, the resistor element, the diode, and the non-volatile rewritable storage portion may be those generally used, and the material and the shape to be used are not particularly limited. Further, the material electrically connecting the above-described components may be any conductive material that can be generally used. The connection method of each component may be any method as long as it can electrically conduct. The width and thickness of the connection part of each component are arbitrary.

<Product tag>
Next, a product tag including the wireless communication device according to the embodiment of the present invention will be described. The article tag includes, for example, a base and the wireless communication device covered by the base.

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

Wireless communication is performed between the product tag and the reader / writer. The reader / writer is a device that reads and writes data with respect to a product tag wirelessly. The reader / writer exchanges data with the product tag at the time of distribution process or settlement of the product. The reader / writer may be, for example, a portable type or a stationary type installed at a cash register. A well-known reader / writer can be used for the product tag according to the embodiment of the present invention.

The commodity tag according to the embodiment of the present invention has an identification information reply function. This is a function in which the product tag wirelessly sends the individual identification information stored therein when it receives a command for requesting transmission of the individual identification information from a predetermined reader / writer. Individual identification information of each tag is transmitted from a large number of product tags by one command from the reader / writer. This function enables, for example, non-contact identification of a large number of products simultaneously at the checkout of products. Therefore, it is possible to facilitate and expedite the settlement process as compared with the identification by the barcode.

Also, for example, at the time of accounting of a product, the reader / writer can transmit product information read from a product tag to a POS (Point of sale system, point-of-sales information management) terminal. With this function, the POS terminal can also carry out sales registration of a product specified by the product information, so that inventory management can be facilitated and speeded up.

Hereinafter, the present invention will be more specifically described based on examples. The present invention is not construed as being limited to the following examples.

The molecular weight of the polymer was measured as follows. The sample is filtered through a 0.45 μm membrane filter, and then GPC (GEL PERMEATION CHROMATOGRAPHY: gel permeation chromatography, Tosoh HLC-8220GPC) (developing solvent: chloroform or tetrahydrofuran, developing speed: 0.4 mL / min) Using, it calculated | required by conversion with a polystyrene standard sample.

The film thickness was measured as follows. Among the images obtained using SEM for the sample, the film thickness of 10 places randomly selected from the second insulating layer portion or the barrier layer located on the semiconductor layer is calculated, and the value of the arithmetic average is calculated. I asked.

The water vapor permeability was calculated based on JIS K 7129 2008 (how to determine the water vapor permeability of plastic films and sheets). The conditions are 25 ° C. and 90% RH. The measurement sample (test piece) has a film or sheet shape and is adjusted to an appropriate size in the case of a sample that can be measured by size adjustment, and film formation on a polyethylene terephthalate film in other cases. Prepared.

Preparation Example 1 of Semiconductor Solution; Semiconductor Solution A
Compound [60] was synthesized by the method shown in Formula 1.

Compound (1-a) (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.3 g and bromine (manufactured by Wako Pure Chemical Industries, Ltd.) 10 g are added to 150 mL of 48% hydrobromic acid and stirred at 120 ° C. for 3 hours did. After cooling to room temperature, the precipitated solid was filtered through a glass filter and washed with 1000 mL of water and 100 mL of acetone. The obtained solid was vacuum dried at 60 ° C. to obtain 6.72 g of compound (1-b).

10.2 g of the compound (1-c) was dissolved in 100 mL of dimethylformamide, 9.24 g of N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere. To the resulting solution, 200 mL of water, 200 mL of n-hexane and 200 mL of dichloromethane were added, and the organic layer was separated. The obtained organic layer was washed with 200 mL of water and then dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: hexane) to obtain 14.4 g of compound (1-d).

14.2 g of the compound (1-d) was dissolved in 200 mL of tetrahydrofuran and cooled to -80.degree. After adding 35 mL of n-butyllithium (1.6 M hexane solution) (manufactured by Wako Pure Chemical Industries, Ltd.) to the solution, the temperature was raised to -50.degree. C. and cooled again to -80.degree. Thereto, 13.6 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (manufactured by Wako Pure Chemical Industries, Ltd.) is added, the temperature is raised to room temperature, and a nitrogen atmosphere is established. Stir under for 4 hours. To the resulting solution, 200 mL of 1N aqueous ammonium chloride solution and 200 mL of ethyl acetate were added, and the organic layer was separated. The obtained organic layer was washed with 200 mL of water and then dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: hexane / dichloromethane) to obtain 14.83 g of compound (1-e).

14.83 g of the compound (1-e) and 6.78 g of 5,5'-dibromo-2,2'-bithiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 200 mL of dimethylformamide, and further under a nitrogen atmosphere Then, 26.6 g of potassium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.7 g of [bis (diphenylphosphino) ferrocene] dichloropalladium (manufactured by Aldrich) were added, and the mixture was stirred at 100 ° C. for 4 hours. To the resulting solution, 500 mL of water and 300 mL of ethyl acetate were added, and the organic layer was separated. The obtained organic layer was washed with 500 mL of water and then dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: hexane) to obtain 4.53 g of compound (1-f).

4.53 g of compound (1-f) was dissolved in 40 mL of tetrahydrofuran and cooled to -80.degree. After adding 6.1 mL of n-butyllithium (1.6 M solution in hexane) to the solution, the temperature was raised to -5.degree. C. and cooled again to -80.degree. Thereto, 2.3 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added, and the temperature was raised to room temperature and stirred for 2 hours under a nitrogen atmosphere. To the resulting solution, 150 mL of 1N aqueous ammonium chloride solution and 200 mL of ethyl acetate were added, and the organic layer was separated. The obtained organic layer was washed with 200 mL of water and then dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: dichloromethane / hexane) to give 2.31 g of a compound (1-g).

0.498 g of compound (1-b) and 2.31 g of compound (1-g) are added to 17 mL of dimethylformamide, and further 2.17 g of potassium phosphate and [bis (diphenylphosphino)] under a nitrogen atmosphere 0.14 g of ferrocene] dichloropalladium (manufactured by Aldrich) was added, and the mixture was stirred at 90 ° C. for 7 hours. To the resulting solution, 200 mL of water and 100 mL of chloroform were added, and the organic layer was separated. The obtained organic layer was washed with 200 mL of water and then dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: dichloromethane / hexane) to give 1.29 g of compound (1-h). The results of ¹ H-NMR analysis of compound (1-h) are shown.
¹ H-NMR (CD ₂ Cl ₂ , (d = ppm)): 8.00 (s, 2 H), 7.84 (s, 2 H), 7.20-7.15 (m, 8 H), 7. 04 (d, 2H), 6.95 (d, 2H), 2.88 (t, 4H), 2.79 (t, 4H), 1.77-1.29 (m, 48H), 0.88 (M, 12H).

0.734 g of the compound (1-h) was dissolved in 15 mL of chloroform, 0.23 g of N-bromosuccinimide and 10 mL of dimethylformamide were added, and the mixture was stirred at room temperature for 9 hours under a nitrogen atmosphere. 100 mL of water and 100 mL of chloroform were added to the obtained solution, and the organic layer was separated. The obtained organic layer was washed with 200 mL of water and then dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: dichloromethane / hexane) to give 0.58 g of compound (1-i).

0.5 g of compound (1-j), 0.85 g of bis (pinacolato) diboron (manufactured by BASF), and 0.86 g of potassium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) are added to 7 mL of 1,4-dioxane; Furthermore, under a nitrogen atmosphere, 0.21 g of [bis (diphenylphosphino) ferrocene] dichloropalladium was added and the mixture was stirred at 80 ° C. for 7 hours. To the resulting solution, 100 mL of water and 100 mL of ethyl acetate were added, and the organic layer was separated. The obtained organic layer was washed with 100 mL of water and then dried over magnesium sulfate. The resulting solution was purified by column chromatography (filler: silica gel, eluent: dichloromethane) to give 57 mg of compound (1-k).

93 mg of compound (1-i) and 19.3 mg of compound (1-k) were dissolved in 6 mL of toluene. To this were added 2 mL of water, 0.18 g of potassium carbonate, 7.7 mg of tetrakis (triphenylphosphine) palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 drop of Aliquat® 336 (manufactured by Aldrich), The mixture was stirred at 100 ° C. for 25 hours under a nitrogen atmosphere. Then, 40 mg of phenylboronic acid was added and stirred at 100 ° C. for 7 hours. To the resulting solution was added 50 mL of methanol, and the resulting solid was collected by filtration and washed sequentially with methanol, water, methanol and acetone. The obtained solid was dissolved in chloroform, passed through a silica gel short column (eluent: chloroform) and concentrated to dryness to obtain 30 mg of Compound [60]. The molecular weight of the compound [60] was measured by the above method to find that the weight average molecular weight was 4367, the number average molecular weight was 3475, and the degree of polymerization n was 3.1.

To a 10 mL solution of compound [60] 2.0 mg in chloroform was added 1.0 mg of CNT1 (CNI company, single-layer CNT, purity 95%), and while cooling with ice, an ultrasonic homogenizer (VCX manufactured by Tokyo Rika Kikai Co., Ltd.) The mixture was ultrasonically stirred for 4 hours at an output of 20% using -500) to obtain CNT dispersion A (a concentration of CNT complex to solvent: 0.96 g / L).

Next, a semiconductor solution for forming a semiconductor layer was produced. The CNT dispersion A was filtered using a membrane filter (pore diameter: 10 μm, diameter: 25 mm, manufactured by Millipore Corporation, omnipore membrane) to remove a CNT complex having a length of 10 μm or more. After 5 mL of o-DCB (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained filtrate, chloroform, which is a low boiling point solvent, was distilled off using a rotary evaporator to obtain CNT dispersion liquid B. Three mL of o-DCB was added to 1 mL of the CNT dispersion B to obtain a semiconductor solution A (a concentration of the CNT complex relative to a solvent: 0.03 g / L).

Preparation Example 1 of Composition; Gate Insulating Layer Solution A
61.29 g (0.45 mol) of methyltrimethoxysilane, 12.31 g (0.05 mol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 99.15 g (0.5 mol) of phenyltrimethoxysilane Mol) was dissolved in 203.36 g of propylene glycol monobutyl ether (boiling point 170 ° C.), to which 54.90 g of water and 0.864 g of phosphoric acid were added while stirring. The resulting solution was heated at a bath temperature of 105 ° C. for 2 hours, and the internal temperature was raised to 90 ° C. to distill off a component consisting mainly of by-produced methanol. Next, the mixture was heated at a bath temperature of 130 ° C. for 2.0 hours, the internal temperature was raised to 118 ° C., and a component consisting mainly of water and propylene glycol monobutyl ether was distilled off. Thereafter, the solution was cooled to room temperature to obtain a polysiloxane solution A having a solid concentration of 26.0% by weight. The molecular weight of the obtained polysiloxane was measured by the above method, and the weight average molecular weight was 6000.

10 g of the obtained polysiloxane solution A and aluminum bis (ethylacetoacetate) mono (2,4-pentanedionate) (trade name “aluminum chelate D”, manufactured by Kawaken Fine Chemical Co., Ltd., hereinafter referred to as aluminum chelate D) 13 .0 g and 42.0 g of propylene glycol monoethyl ether acetate (hereinafter referred to as PGMEA) were mixed, and stirred at room temperature for 2 hours to obtain a gate insulating layer solution A. The content of the above-mentioned polysiloxane in this solution was 20 parts by weight with respect to 100 parts by weight of aluminum chelate D.

Preparation Example 2 of Composition; Solution A for Preparation of Second Insulating Layer
DISPERBYK 2022 (manufactured by Bick Chemie Japan Ltd., a polymer having a unit structure represented by the general formula (3) and further having a unit structure represented by the general formula (4). A unit structure represented by the general formula (4) And a unit structure represented by the general formula (3) = 78/22) 10.0 g of PGMEA was dissolved in 10.0 g of PGMEA to obtain a solution A for producing a second insulating layer.

Preparation Example 3 of Composition; Solution B for Preparation of Second Insulating Layer
BYK 6919 (manufactured by Bick Chemie Japan Ltd., a polymer having a unit structure represented by the general formula (3) and further having a unit structure represented by the general formula (4). A unit structure represented by the general formula (4) And a unit structure represented by the general formula (3) = 55/45) 10.0 g of PGMEA was dissolved in 10.0 g of PGMEA to obtain a solution B for producing a second insulating layer.

Preparation Example 4 of Composition; Solution C for Preparation of Second Insulating Layer
0.60 g of dicyclohexylmethylamine (made by Tokyo Chemical Industry Co., Ltd.) was added to 10.0 g of a solution B for producing a second insulating layer to obtain a solution C for producing a second insulating layer.

Preparation Example 5 of Composition; Solution D for Preparation of Second Insulating Layer
0.60 g of quinuclidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 10.0 g of a solution B for producing a second insulating layer to obtain a solution D for producing a second insulating layer.

Preparation Example 6 of Composition; Solution E for Preparation of Second Insulating Layer
0.60 g of DBU (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to 10.0 g of the second insulating layer solution B to obtain a solution E for producing a second insulating layer.

Preparation Example 7 of Composition; Solution F for Preparation of Second Insulating Layer
3.0 g of polymethyl methacrylate (PMMA, manufactured by Mitsubishi Rayon Co., Ltd.) was dissolved in 10.0 g of PGMEA to obtain a solution F for producing a second insulating layer.

Preparation Example 8 of Composition: Solution A for Preparation of Barrier Layer
2.5 g of cycloolefin polymer (manufactured by Nippon Zeon) was dissolved in 7.5 g of decahydronaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a solution A for producing a barrier layer.

Preparation Example 9 of Composition: Solution B for Preparation of Barrier Layer
0.13 g of cycloolefin polymer (manufactured by Nippon Zeon) was dissolved in 9.8 g of decahydronaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a solution B for producing a barrier layer.

Example 1
The semiconductor element of the structure shown in FIG. 1 was produced. A gate electrode 2 was formed on a glass substrate 1 (film thickness 0.7 mm) by vacuum evaporation of chromium 5 nm thick and gold 50 nm thick through a mask by resistance heating. Next, the gate insulating layer solution A was spin coated (2000 rpm × 30 seconds) on the above substrate, and heat treated at 200 ° C. for 1 hour in a nitrogen stream to form a gate insulating layer 3 with a thickness of 600 nm. Next, gold was vacuum-deposited to a thickness of 50 nm through a mask by resistance heating to form a source electrode 5 and a drain electrode 6. Next, 1 μL of the semiconductor solution A is dropped between the source electrode 5 and the drain electrode 6, air-dried at 30 ° C. for 10 minutes, and then heat-treated at 150 ° C. for 30 minutes under a nitrogen stream on a hot plate. The semiconductor layer 4 was formed. Next, 5 μL of a solution of polyallylamine (PAA-05, manufactured by NITTOBO CO., LTD.) Is dropped on the semiconductor layer 4 so as to cover the semiconductor layer 4 and heat-treated at 110 ° C. for 15 minutes under a nitrogen stream to form a second insulation. A layer was formed. Thus, a semiconductor element was obtained. The width (channel width) of the source / drain electrode of this semiconductor element was 200 μm, and the distance between the source / drain electrode (channel 4 length) was 20 μm. The film thickness of the second insulating layer in this semiconductor element was 38 μm.

Next, the source-drain current (Id) -source-drain voltage (Vsd) characteristics when the gate voltage (Vg) was changed were measured. In the measurement, semiconductor characteristic evaluation system 4200-SCS (manufactured by Keithley Instruments, Inc.) was used, and the inside of the measurement chamber was set to 30% RH. The mobility of the linear region was determined from the change in the value of Id at Vsd = + 5 V when changing to Vg = + 30 to −30 V. Next, the inside of the measurement chamber was set to 50% RH, and the same measurement as in the case of 30% RH was performed. Next, the inside of the measurement chamber was set to 70% RH, and the same measurement as in the case of 30% RH was performed. The results are shown in Table 1.

Example 2
A semiconductor element was fabricated and mobility was evaluated in the same manner as in Example 1 except that the solution A for producing the second insulating layer was used instead of the polyallylamine solution. The film thickness of the second insulating layer in this semiconductor element was 42 μm.

Example 3
A semiconductor element was fabricated and mobility was evaluated in the same manner as in Example 1 except that the solution B for producing the second insulating layer was used instead of the polyallylamine solution. The film thickness of the second insulating layer in this semiconductor element was 41 μm.

Example 4
A semiconductor element was produced in the same manner as in Example 1 except that the solution C for producing the second insulating layer was used instead of the polyallylamine solution, and the mobility was evaluated. The film thickness of the second insulating layer in this semiconductor element was 40 μm.

Example 5
A semiconductor element was fabricated and mobility was evaluated in the same manner as in Example 1 except that the solution D for producing the second insulating layer was used instead of the polyallylamine solution. The film thickness of the second insulating layer in this semiconductor element was 43 μm.

Example 6
A semiconductor element was produced in the same manner as in Example 1 except that the solution E for producing the second insulating layer was used instead of the polyallylamine solution, and the mobility was evaluated. The film thickness of the second insulating layer in this semiconductor element was 42 μm.

Example 7
A second insulating layer was formed in the same manner as in Example 6. Then, 10 μL of solution A for producing a barrier layer was dropped so as to cover the second insulating layer, and heat treatment was performed at 90 ° C. for 15 minutes in a nitrogen stream to form a barrier layer. Thus, a semiconductor element was obtained. In this semiconductor element, the film thickness of the second insulating layer was 45 μm, and the film thickness of the barrier layer was 98 μm.

Example 8
A semiconductor element was produced in the same manner as in Example 7 except that a fluorine resin solution (CYTOP 809A, manufactured by Asahi Glass Co., Ltd.) was used instead of the solution A for producing a barrier layer, and the mobility was evaluated. In this semiconductor element, the film thickness of the second insulating layer was 41 μm, and the film thickness of the barrier layer was 9 μm.

Example 9
A second insulating layer was formed in the same manner as in Example 6. Subsequently, 10 μL of solution B for preparing a barrier layer was dropped so as to cover the second insulating layer, and heat treatment was performed at 90 ° C. for 15 minutes in a nitrogen stream to form a barrier layer. Thus, a semiconductor element was obtained. In this semiconductor element, the film thickness of the second insulating layer was 43 μm, and the film thickness of the barrier layer was 5 μm.

Comparative Example 1
A semiconductor element was produced in the same manner as in Example 1 except that the solution F for producing the second insulating layer was used instead of the polyallylamine solution, and the mobility was evaluated. The film thickness of the second insulating layer in this semiconductor element was 40 μm.

Reference Signs List 1 substrate 2 gate electrode 3 gate insulating layer 4 semiconductor layer 5 source electrode 6 drain electrode 7 nanocarbon 8 second insulating layer 9 barrier layer 50 antenna

Claims

A substrate,
A source electrode, a drain electrode and a gate electrode,
A semiconductor layer in contact with the source electrode and the drain electrode;
A gate insulating layer which insulates the semiconductor layer from the gate electrode;
An n-type semiconductor element comprising: a second insulating layer in contact with the semiconductor layer on the side opposite to the gate insulating layer with respect to the semiconductor layer;
The semiconductor layer contains nanocarbon,
An n-type semiconductor device characterized in that the second insulating layer contains a polymer having a structure represented by the general formula (1) in at least a part of a side chain.

(In the general formula (1), R 1 and R 2 each independently represent one or more atoms selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom R 3 and R 4 each independently represent a hydrogen atom or a group represented by the following general formula (2).)

(In the general formula (2), R 5 to R 7 each independently represent one or more atoms selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom Group is shown)
The n-type semiconductor device according to claim 1, wherein the polymer having a structure represented by the general formula (1) in a side chain is a polymer having a unit structure represented by the general formula (3).

(In the general formula (3), R 1 to R 4 each have the same meaning as described in the general formula (1). R 8 is a single bond or a carbon atom, an oxygen atom, a nitrogen atom, or silicon R 9 represents a group constituted by one or more types of atoms selected from atoms, phosphorus atoms and sulfur atoms R 9 is selected from hydrogen atoms, carbon atoms, nitrogen atoms, oxygen atoms, silicon atoms, phosphorus atoms and sulfur atoms Indicates a group composed of one or more atoms.)
The n-type semiconductor device according to claim 2, wherein the polymer having a structure represented by the general formula (1) in a side chain further has a unit structure represented by the general formula (4).

(In the general formula (4), Y is a group consisting of an amide group, an ester group, a urea group, a carbonyl group, an imide group, a ureido group, a thioamide group, a thioester group, a thiourea group, a thiocarbonyl group, a thioimide group and a thioureido group R 10 represents a group constituted by one or more atoms selected from hydrogen atom, carbon atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom, and R 11 represents a single bond. Or a divalent group constituted by one or more kinds of atoms selected from hydrogen atom, carbon atom, oxygen atom, silicon atom, phosphorus atom and sulfur atom, R 12 is carbon atom, oxygen atom, silicon Indicates a group constituted by one or more kinds of atoms selected from an atom, a phosphorus atom and a sulfur atom.)
The n-type semiconductor device according to any one of claims 1 to 3, wherein the film thickness of the second insulating layer is 500 nm or more.
The n-type semiconductor device according to any one of claims 1 to 4, wherein the second insulating layer further contains an electron donating compound having one or more atoms selected from a nitrogen atom and a phosphorus atom.
The n-type semiconductor device according to claim 5, wherein the electron donating compound is a compound having a nitrogen atom.
The n-type semiconductor device according to claim 6, wherein the electron donating compound is a compound containing a ring structure containing a nitrogen atom.
The semiconductor device according to any one of claims 1 to 7, further comprising a layer having a water vapor transmission rate of 20 g / (m 2 · 24 h) or less (referred to as a barrier layer) on the second insulating layer.
The n-type semiconductor device according to claim 8, wherein the barrier layer contains at least one selected from the group consisting of a fluorine resin, a chlorine resin, a nitrile resin, a polyester resin, and a polyolefin resin.
The n-type semiconductor device according to any one of claims 1 to 9, wherein the nanocarbon is a carbon nanotube.
11. The n-type semiconductor device according to claim 10, wherein a conjugated polymer is attached to at least a part of the surface of the carbon nanotube.
The method for producing an n-type semiconductor device according to any one of claims 1 to 11, wherein a composition containing a polymer having a structure represented by the general formula (1) in at least a part of a side chain and a solvent is applied. And manufacturing the second insulating layer by drying.
The method for producing an n-type semiconductor device according to claim 12, wherein the step of forming the semiconductor layer includes the steps of applying a solution consisting of a component of the semiconductor layer and a solvent, and drying the solution.
A wireless communication device comprising at least the semiconductor element according to any one of claims 1 to 11 and an antenna.
A merchandise tag using the wireless communication device according to claim 14.