JP6856174B1 - Carbon nanotube dispersion liquid, manufacturing method of semiconductor device using it, and manufacturing method of wireless communication device - Google Patents

Abstract

An object of the present invention is to provide a carbon nanotube dispersion liquid that can be applied to a desired position with high accuracy by inkjet, and a carbon nanotube composite in which a conjugated polymer is attached to at least a part of the surface of the carbon nanotube and a solvent. A carbon nanotube dispersion liquid containing at least and, wherein the conjugated polymer has a side chain represented by the general formula (1), the solvent is a single or mixed solvent, and the viscosity is 5. The main purpose is a carbon nanotube dispersion liquid containing a solvent having a boiling point of about 40 cP, a boiling point of 150 to 290 ° C., or a vapor pressure of 0.9 to 500 Pa. (In the general formula (1), R1 represents an alkylene group or a cycloalkylene group. X represents a single bond, an alkenylene group, etc. A represents a hydroxy group, an alkylsulfanil group, etc.)

Description

The present invention relates to a carbon nanotube dispersion liquid, a method for manufacturing a semiconductor device using the same, and a method for manufacturing a wireless communication device.

In recent years, as a non-contact type tag, the development of a wireless communication system using RFID (Radio Frequency Identification) technology has been promoted. In an RFID system, wireless communication is performed between a wireless transmitter / receiver called a reader / writer and an RFID tag.

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

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

For example, in a transistor in a drive circuit in an IC chip, it is conceivable to use an organic semiconductor to which an inkjet technique, a spin coating technique, or the like can be applied as a material for a semiconductor layer. Therefore, field effect transistors (hereinafter referred to as FETs) using carbon nanotubes (CNTs) and organic semiconductors have been actively studied in place of conventional inorganic semiconductors (for example, Patent Documents 1 and 2 and Non-Patent Documents 1). See ~ 2). This movement is observed not only in RFID tags but also in semiconductors used as, for example, sensors and thin film transistor (TFT) arrays for displays (see, for example, Patent Document 3).

International Publication No. 2009/139339 International Publication No. 2017/130863 International Publication No. 2015/12186

Nano Letters. 16, p. 5120-5128 (2016) Applied Physics Letters. 112, p. 033103 (2018)

Transistors are arranged in drive circuits and TFT arrays, and a technique for forming a semiconductor layer at each transistor position is required. As a candidate technique, there is a technique of forming a semiconductor layer by applying a solution of a semiconductor layer material to a desired position by inkjet and drying it.

However, the carbon nanotube dispersion liquids produced by the techniques described in Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 have poor coating properties by inkjet, and satellites (spattering of inkjet coating liquid) are generated and the coating position. There is a problem that a phenomenon such as insufficient accuracy occurs and the variation in transistor characteristics becomes large.

The inventors have found that this is due to the use of low viscosity solvents such as toluene (viscosity 1.5 cP) and N-methylpyrrolidone (viscosity 1.9 cP). However, when a thickener is added in order to maintain a suitable viscosity range, when a semiconductor device is formed, there is a problem that conductivity is inhibited by the thickener and the device characteristics are insufficient. Another approach is to use a solvent of suitable viscosity, but conventional CNT complexes have not been able to disperse well in a solvent of such viscosity.

Therefore, an object of the present invention is to provide a carbon nanotube dispersion liquid that can be applied to a desired position with high accuracy by inkjet.

In order to solve the above problems, the present invention has the following configurations.
That is, the present invention
It is a carbon nanotube dispersion liquid containing at least a carbon nanotube complex in which a conjugate polymer is attached to at least a part of the surface of the carbon nanotubes and a solvent, and the conjugate polymer is represented by the general formula (1). The solvent is a single or mixed solvent, the single or mixed solvent has a viscosity of 5 to 40 cP, and the single or mixed solvent has a boiling point of 150 to 290 ° C. It is a carbon nanotube dispersion liquid containing a certain solvent or a solvent having a steam pressure of 0.9 to 500 Pa.

(In the general formula (1), R ¹ represents an alkylene group or a cycloalkylene group. X represents a single bond, an alkenylene group, an alkynylene group, an arylene group or a heteroarylene group. A represents a hydroxy group or an alkylsulfanyl. A group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an N-alkylcarbonylamino group, an N-alkyl-N-alkylcarbonylamino group, or a group represented by the general formula (2). Show.)

(In the general formula (2), R ² represents an alkylene group. R ³ represents a hydrogen atom or a hydroxy group. M represents an integer of 1 or more.)

According to the present invention, it is possible to obtain a carbon nanotube dispersion liquid that can be applied to a desired position with high accuracy by inkjet. Further, it is possible to provide a method for manufacturing a semiconductor element and a wireless communication device using the same.

Schematic cross-sectional view showing a semiconductor device formed by using the CNT dispersion liquid according to the embodiment of the present invention. Schematic cross-sectional view showing a semiconductor device formed by using the CNT dispersion liquid according to the embodiment of the present invention. Schematic cross-sectional view showing a semiconductor device formed by using the CNT dispersion liquid according to the embodiment of the present invention. Block diagram showing an example of a wireless communication device

Hereinafter, preferred embodiments of a carbon nanotube dispersion liquid, a method for manufacturing a semiconductor device using the carbon nanotube dispersion liquid, and a method for manufacturing a wireless communication device will be described in detail. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented according to an object and an application.

<Carbon nanotube dispersion liquid>
The carbon nanotube (hereinafter referred to as CNT) dispersion liquid is a CNT composite in which a conjugated polymer having a side chain represented by the general formula (1) described later is attached to at least a part of the surface of the CNT, and a composition described later. And at least a solvent having properties.

(CNT complex)
In the CNT complex, a conjugated polymer having a side chain represented by the general formula (1) described later is attached to at least a part of the surface of the CNT.

By adhering the conjugated polymer to at least a part of the surface of the CNT, the CNT can be uniformly dispersed in the solution without impairing the high electrical properties of the CNT. If a solution in which CNTs are uniformly dispersed is used, it becomes possible to form a uniformly dispersed CNT film 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 a state in which a part or the whole of the surface of the CNT is covered with the conjugated polymer. It is presumed that the conjugated polymer can coat CNTs because the interaction occurs due to the overlap of the π-electron clouds derived from the conjugated structures of both.

Whether or not the CNT is coated with the conjugated polymer can be determined from the reflected color of the CNT. The reflected color of the coated CNT is different from the reflected color of the uncoated CNT and is close to the reflected color of the conjugated polymer. Quantitatively, elemental analysis such as X-ray photoelectron spectroscopy (XPS) can be used to confirm the presence of deposits on the CNTs and to measure the weight ratio of the deposits to the CNTs. The conjugated polymer preferably covers 5% or more and 90% or less of the surface of the CNT, more preferably 70% or less, and further preferably 50% or less.

As a method of adhering the conjugated polymer to the CNT, (I) a method of adding CNT to the molten conjugated polymer and mixing it, and (II) dissolving the conjugated polymer in a solvent and incorporating it into the CNT. A method of adding and mixing CNTs, (III) a method of pre-dispersing CNTs in a solvent by ultrasonic waves or the like, and then adding and mixing a conjugated polymer there, (IV) a conjugated polymer in a solvent. And CNT are put in, and a method of irradiating this mixing system with ultrasonic waves to mix the polymer can be mentioned. In the present invention, any method may be used, and a plurality of methods may be combined.

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

Further, it is more preferable that the CNT contains 80% by weight or more of the semiconductor type CNT. More preferably, it contains 90% by weight or more of semiconductor-type CNTs, and particularly preferably 95% by weight or more of semiconductor-type CNTs. As a method for containing 80% by weight or more of the semiconductor type CNT in the CNT, a known method can be used. For example, a method of ultracentrifugating in the presence of a density gradient agent, a method of selectively adhering a specific compound to the surface of a semiconductor-type or metal-type CNT and separating using the difference in solubility, a difference in electrical properties. There is a method of separating by electrophoresis or the like using the above. Examples of the method for measuring the content of semiconductor-type CNTs in CNTs include 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.

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

The average length of CNTs is the average value of the lengths of 20 randomly picked CNTs. As a method for measuring the average length of CNTs, 20 CNTs are randomly picked up from images obtained by an atomic force microscope, a scanning electron microscope, a transmission electron microscope, etc., and the average value of their lengths is obtained. There is a way to obtain.

Generally, commercially available CNTs have a distribution in length, and may include CNTs longer than the distance between electrodes. Therefore, it is preferable to add a step of making the CNT shorter than the distance between the electrodes. For example, a method of cutting CNTs into short fibers by acid treatment with nitric acid, sulfuric acid or the like, ultrasonic treatment, or freeze pulverization method is effective. Further, it is more preferable to use the separation by a filter together in terms of improving the purity of CNTs.

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

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

(Conjugated polymer)
In the present invention, the conjugated polymer refers to a compound in which the repeating unit has a conjugated structure and the degree of polymerization is 2 or more. Examples of the conjugated polymer include polythiophene-based polymers, polypyrrole-based polymers, polyaniline-based polymers, polyacetylene-based polymers, poly-p-phenylene-based polymers, and poly-p-phenylene vinylene-based polymers. , Not particularly limited. As the polymer, a polymer in which a single monomer unit is lined up is preferably used, but a polymer in which different monomer units are block-copolymerized, a random-copolymerized polymer, and a graft-polymerized polymer are also preferably used.

Among the above polymers, in the present invention, a conjugated polymer containing a fluorene unit or a thiophene unit in a repeating unit is preferable from the viewpoint of easy adhesion to CNTs and easy formation of CNT complexes. Further, those containing a condensed heteroaryl unit having a nitrogen-containing double bond in the ring in the repeating unit are more preferable.

Condensed heteroaryl units having a nitrogen-containing double bond in the ring include thienopyrol, pyrolotiazole, pyropyridazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, benzothiadiazole, quinoline, quinoxalin, benzotriazole, thienooxazole. , Thienopyridine, thienothiazine, thienopyrazine and the like. Of these, the benzothiadiazole unit or the quinoxaline unit is particularly preferable. By having these units, the adhesion between the CNT and the conjugated polymer is increased, and the CNT can be dispersed better.

In the present invention, the conjugated polymer has a side chain represented by the general formula (1).

In the general formula (1), R ¹ represents an alkylene group or a cycloalkylene group. X represents a single bond, an alkenylene group, an alkynylene group, an arylene group or a heteroarylene group. A is a hydroxy group, an alkylsulfanyl group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an N-alkylcarbonylamino group, an N-alkyl-N-alkylcarbonylamino group, or a general formula ( The group represented by 2) is shown.

In the general formula (2), R ² represents an alkylene group. R ³ represents a hydrogen atom or a hydroxy group. m represents an integer of 1 or more. When m is 2 or more, the alkylene groups may be the same or different from each other.

The CNT complex to which the conjugated polymer having a side chain represented by the general formula (1) is attached has good dispersibility in a solvent. In particular, the CNT complex disperses well in a solvent having a viscosity of about 5 to 40 cP, which is suitable for inkjet coating. It is presumed that this is because the side chain represented by the general formula (1) changed the aspect of the molecular motion of the conjugated polymer in the solvent and improved the compatibility with the solvent having a suitable viscosity.

From the viewpoint of further enhancing the above effect, A is an alkylsulfonyl group, a dialkylaminocarbonyl group, an N-alkyl-N-alkylcarbonylamino group, or a group represented by the general formula (2) and having m of 2 or more. It is preferably represented by an integer. m is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

The alkylene group represents a divalent (two bonding sites) saturated aliphatic hydrocarbon group, and examples thereof include an ethylene group, a propylene group, a butylene group, and a hexylene group. The alkylene group may or may not have a substituent. The number of carbon atoms of the alkylene group is not particularly limited, but in ^{the case of R 1} , it is preferably 1 or more and 20 or less, more preferably 1 or more and 8 or less, and of R ² from the viewpoint of availability and cost. In the case, it is preferably 1 or more and 10 or less, and more preferably 1 or more and 4 or less.

The cycloalkylene group represents a divalent saturated alicyclic hydrocarbon group, and examples thereof include a cyclopropylene group, a cyclobutylene group, a cyclopentalene group, and a cyclohexylene group. The cycloalkylene group may or may not have a substituent. The number of carbon atoms of the cycloalkylene group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 8 or less, from the viewpoint of availability and cost.

The alkenylene group represents a divalent unsaturated aliphatic hydrocarbon group, and examples thereof include an ethenylene group, a propenylene group, a butenylene group, and a hexenylene group. The alkenylene group may or may not have a substituent. The carbon number of the alkenylene group is not particularly limited, but is preferably 2 or more and 20 or less, and more preferably 2 or more and 8 or less, from the viewpoint of availability and cost.

The alkynylene group represents a divalent unsaturated aliphatic hydrocarbon group, and examples thereof include an ethynylene group, a propynylene group, a butynylene group, and a hexynylene group. The alkynylene group may or may not have a substituent. The carbon number of the alkynylene group is not particularly limited, but is preferably 2 or more and 20 or less, and more preferably 2 or more and 8 or less, from the viewpoint of availability and cost.

The arylene group represents a divalent aromatic hydrocarbon group, and examples thereof include a phenylene group, a naphthylene group, a biphenylene group, a phenanthrylene group, an anthylene group, a terphenylene group, a pyrenylene group, a fluorenylene group, and a peryleneylene group. It may be unchanged or replaced. The carbon number of the arylene group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

The heteroarylene group represents a divalent heteroaromatic ring group, for example, benzofuran, dibenzofuran, benzo, in addition to pyridylene group, pyrazilen group, quinolinylene group, isoquinolylene group, quinoxalylene group, acridinylene group, indolylene group, carbazolylen group and the like. Examples include divalent groups derived from heteroaromatic rings such as thiophene, dibenzothiophene, benzodithiophene, benzosilol and dibenzocilol. It may be unchanged or replaced. The number of carbon atoms of the heteroarylene group is not particularly limited, but is preferably in the range of 2 or more and 30 or less.

The alkylsulfanyl group refers to a functional group in which one of the sulfanyl groups is substituted with an aliphatic hydrocarbon group, such as a methylsulfanyl group, an ethylsulfanyl group, and an n-propylsulfanyl group. The alkylsulfanil group may or may not have a substituent. The number of carbon atoms of the alkylsulfanil group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The alkylsulfinyl group refers to a functional group in which one of the sulfinyl groups is substituted with an aliphatic hydrocarbon group, such as a methylsulfinyl group, an ethylsulfinyl group, and an n-propylsulfinyl group. The alkylsulfinyl group may or may not have a substituent. The number of carbon atoms of the alkylsulfinyl group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The alkylsulfonyl group refers to a functional group in which one of the sulfonyl groups is replaced with an aliphatic hydrocarbon group, such as a methylsulfonyl group, an ethylsulfonyl group, and an n-propylsulfonyl group. The alkylsulfonyl group may or may not have a substituent. The number of carbon atoms of the alkylsulfonyl group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The alkylaminocarbonyl group refers to a functional group in which one of the carbonyl bonds is replaced with an alkylamino group such as a methylamino group or an ethylamino group. The alkylaminocarbonyl group may or may not have a substituent. The number of carbon atoms of the alkylaminocarbonyl group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The dialkylaminocarbonyl group refers to a functional group in which one of the carbonyl bonds is replaced with a dialkylamino group such as a dimethylamino group, a diethylamino group, or an ethylbutylamino group. The dialkylaminocarbonyl group may or may not have a substituent. The number of carbon atoms of the dialkylaminocarbonyl group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The N-alkylcarbonylamino group refers to a functional group in which an alkylcarbonyl group such as an acetyl group is bonded to an amino group. The N-alkylcarbonylamino group may or may not have a substituent. The number of carbon atoms of the N-alkylcarbonylamino group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The N-alkyl-N-alkylcarbonylamino group refers to a functional group in which an aliphatic hydrocarbon group such as a methyl group or an ethyl group and an alkylcarbonyl group such as an acetyl group are bonded to an amino group. The N-alkyl-N-alkylcarbonylamino group may or may not have a substituent. The number of carbon atoms of the N-alkyl-N-alkylcarbonylamino group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. The aliphatic hydrocarbon group may or may not have a substituent. The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more and 20 or less, and more preferably 1 or more and 8 or less, from the viewpoint of availability and cost.

The alkylamino group refers to a functional group in which an aliphatic hydrocarbon group such as a methylamino group, an ethylamino group or an n-propylamino group is bonded to the amino group. The alkylamino group may or may not have a substituent. The number of carbon atoms of the alkylamino group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The dialkylamino group refers to a functional group in which two aliphatic hydrocarbon groups such as a dimethylamino group and a diethylamino group are bonded to the amino group. The two aliphatic hydrocarbon groups may be the same or different from each other. The dialkylamino group may or may not have a substituent. The number of carbon atoms of the dialkylamino group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

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

Specific examples of the conjugated polymer preferably used in the present invention include those having the following structures. However, it is not limited to these.

The side chain described here is a group bonded to the main chain of the conjugated polymer. As the main chain of the conjugated polymer, (1) a conjugated structure and (2) an unsaturated group that forms a ring structure by bonding the conjugated structures to each other correspond to this. As (2), for example, the carbon atom at the 9-position of the fluorene unit is contained in the main chain.

n represents the degree of polymerization of the conjugated polymer, and is preferably in the range of 2 to 1000. Considering the ease of adhesion to CNT, n is more preferably in the range of 3 to 500. In the present invention, the degree of polymerization n is a value obtained from the weight average molecular weight. The weight average molecular weight is measured by using GPC (gel permeation chromatography) and converted using a standard polystyrene sample. Further, from the viewpoint of easy adhesion to CNT, the weight average molecular weight of the conjugated polymer is preferably 1000 or more.

The ratio of the number of units having a side chain represented by the general formula (1) to the total number of units of the conjugated polymer [the number of units having a side chain represented by the general formula (1) / The total number of units of the conjugated polymer] is preferably 1/5 to 1/1. Within this range, compatibility with a solvent having a suitable viscosity can be further improved.

The unit described here contains one of any one selected from the group consisting of an ethenylene group, an ethynylene group, an arylene group and a heteroarylene group as a divalent group contained in the main chain of a conjugated polymer. It is understood as a divalent group. The number of units refers to the number when each of the ethenylene group, ethynylene group, arylene group or heteroarylene group of the main chain in the repeating unit is counted as one unit. "The number of units having a side chain represented by the general formula (1)" means the number of units having a side chain represented by the general formula (1) among the units, and is "a conjugated polymer. "Number of all units" means the total number of units. For example, in the polymer [4], [the number of units having a side chain represented by the general formula (1) / the number of all units of the conjugated polymer] = 1/1, and in the polymer [14], the [general formula]. Number of units having a side chain represented by (1) / Number of all units of conjugated polymer] = 2/3, and polymer [16] has a side chain represented by the general formula (1). Number of units / Number of total units of conjugated polymer] = 4/5.

The conjugated polymer can be synthesized by a known method. For example, as a method of connecting thiophenes to each other, a method of coupling thiophene halide and thiophene boronic acid or thiophene boronic acid ester under a palladium catalyst, or a method of coupling thiophene halide and a thiophene Grignard reagent under a nickel or palladium catalyst. There is a method of coupling with. Further, when connecting the other unit and the thiophene unit, the halogenated other unit and the thiophene unit can be coupled in the same manner. Further, a conjugated polymer can be obtained by introducing a polymerizable functional group into the terminal of the monomer thus obtained and proceeding 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 for removing impurities, for example, a silica gel column chromatography method, a soxley extraction method, a filtration method, an ion exchange method, a chelation method and the like can be used. Two or more of these methods may be combined.

<Solvent>
The CNT dispersion liquid of the present invention has both inkjet coating property and CNT dispersibility by using the above-mentioned conjugated polymer and a solvent having the following composition and characteristics.

The solvent is a single or mixed solvent, the single or mixed solvent has a viscosity of 5-40 cP, and the single or mixed solvent has a boiling point of 150 to 290 ° C. or a vapor pressure of 0.9 to 500 Pa. Contains a solvent.

The viscosity of a single solvent or a mixed solvent refers to the viscosity of the solvent itself when the solvent is a single component, and refers to the viscosity of the mixed solvent when the solvent is a mixed solvent consisting of two or more kinds of solvents.

When a single or mixed solvent contains a solvent having a boiling point of 150 to 290 ° C. or a vapor pressure of 0.9 to 500 Pa, the boiling point or vapor pressure of the solvent itself is in the above range when the solvent is a single component. In the case of a mixed solvent composed of two or more kinds of solvents, it means that at least one boiling point or vapor pressure of each solvent is in the above range.

When the viscosity of the single or mixed solvent is 5 to 40 cP, it is possible to suppress the generation of satellites in the coating by inkjet and improve the accuracy of the coating position. The viscosity of the single or mixed solvent is more preferably 5 to 20 cP, even more preferably 7 to 13 cP. The viscosity of the single or mixed solvent used in the present invention is a value measured at 25 ° C. using a cone plate type viscometer. The method for measuring the viscosity will be described later. The viscosity of the CNT dispersion liquid prepared by dispersing the CNT complex in a single solvent or a mixed solvent is usually about the same as the viscosity of the solvent used.

Specific examples of a single solvent having a viscosity of 5 to 40 cP include benzyl benzoate, α-tetralone, dimethyl phthalate, diethyl phthalate, 1-methoxynaphthalene, methyl o-anisate, benzyl alcohol, and ethylene glycol monophenyl. Examples thereof include ether, propylene glycol monophenyl ether, phenyldiglycol, N-octylpyrrolidone, N-cyclohexylpyrrolidone, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether and triacetin. Further, the single or mixed solvent contains a solvent having a boiling point of 150 to 290 ° C. or a vapor pressure of 0.9 to 500 Pa, so that the CNT dispersion liquid dries at the coating port of the inkjet head. Clogging can be avoided, and the CNT dispersion liquid discharged onto the substrate can be dried by a drying step. The boiling point is more preferably 170 to 270 ° C. The vapor pressure is more preferably 1.1 to 400 Pa. The vapor pressure is a value at 20 ° C.

Specific examples of solvents having a boiling point or vapor pressure in the above range include, for example, 4-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, 1-bromo-2-chlorobenzene, 1,2,4-trichlorobenzene, and the like. 2,3-Dichlorotoluene, 1-chloronaphthalene, 3-phenoxytoluene, veratrol, α-tetralone, dimethyl phthalate, 1-methoxynaphthalene, methyl o-anisate, benzyl alcohol, ethylene glycol monophenyl ether, propylene glycol mono Examples thereof include phenyl ether, phenyl diglycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol methyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triacetin and terpineol. When used as a mixed solvent, the mixed solvent preferably contains 5% by weight or more of a halogen-based aromatic solvent in the total solvent. By containing 5% by weight or more of the halogen-based aromatic solvent in the total solvent, it becomes easy to adjust the polarity and viscosity of the solvent in a preferable range. In addition, the halogen-based aromatic solvent has good compatibility with CNTs and can improve CNT dispersibility. More preferably, the halogen-based aromatic solvent is contained in the total solvent in an amount of 5% by weight or more and 50% by weight or less, more preferably 15% by weight or more and 35% by weight or less.

Examples of the halogen-based aromatic solvent include chlorobenzene, 4-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, 1-bromo-2-chlorobenzene, 1,2,4-trichlorobenzene, and 2,3-dichlorotoluene. , 1-chloronaphthalene and the like.

When the above viscosity range is obtained with a mixed solvent of a halogen-based aromatic solvent and another solvent, the other solvent includes, for example, benzyl benzoate, veratrol, α-tetralone, dimethyl phthalate, diethyl phthalate, 1-. Ethylenenaphthalene, methyl o-anisate, benzyl alcohol, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, phenyldiglycol, N-octylpyrrolidone, N-cyclohexylpyrrolidone, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene Glycol monobutyl ether, triacetin and the like can be mentioned. Among them, the other solvent is preferably an aromatic solvent or a terpene solvent. The solvent is particularly compatible with the conjugated polymer of the present invention and can improve the CNT dispersibility. Preferred are, for example, benzyl benzoate, α-tetralone, dimethyl phthalate, diethyl phthalate, 1-methoxynaphthalene, methyl o-anisate, benzyl alcohol, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, phenyldiglycol. , Terpineol, etc.

More specific examples include, for example, dimethyl phthalate / o-dichlorobenzene = 75% by weight / 25% by weight (viscosity 7.8 cP), ethylene glycol monophenyl ether / o-dichlorobenzene = 75% by weight / 25% by weight. % (Viscosity 8.5 cP), propylene glycol monophenyl ether / o-dichlorobenzene = 75% by weight / 25% by weight (viscosity 9.6 cP), ethylene glycol monophenyl ether / 1-chloronaphthalene = 75% by weight / 25% by weight % (Viscosity 13.7 cP), phenyldiglycol / o-dichlorobenzene = 75% by weight / 25% by weight (viscosity 12.8 cP), phenyldiglycol / o-dichlorobenzene = 90% by weight / 10% by weight (viscosity 21) .8 cP), triethylene glycol monobutyl ether / o-dichlorobenzene = 75% by weight / 25% by weight (viscosity 6.7 cP), N-cyclohexylpyrrolidone / o-dichlorobenzene = 90% by weight / 10% by weight (viscosity 9. 0 cP), terpineol / o-dichlorobenzene = 75% by weight / 25% by weight (viscosity 8.9 cP) and the like.

<Semiconductor element>
The semiconductor element obtained by the method for manufacturing a semiconductor element according to the embodiment of the present invention includes 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. A semiconductor device including a gate insulating layer that insulates the gate electrode. The semiconductor layer is formed by using the CNT dispersion liquid of the present invention, and is formed on at least a part of the surface of the CNT by the general formula (1). It contains a CNT complex to which a conjugate semiconductor having a side chain represented by is attached.

FIG. 1 is a schematic cross-sectional view showing a first example of a semiconductor device. A gate electrode 2 formed on an insulating base material 1, a gate insulating layer 3 covering the gate electrode 2, a source electrode 5 and a drain electrode 6 provided on the gate electrode 2, and a semiconductor layer provided between the electrodes. 4 and. The semiconductor layer 4 includes a CNT complex 7.

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

FIG. 2 is a schematic cross-sectional view showing a second example of the semiconductor element. A gate electrode 2 formed on an insulating base material 1, a gate insulating layer 3 covering the gate electrode 2, a semiconductor layer 4 provided on the gate electrode 2, a source electrode 5 and a drain electrode 6 formed on the gate electrode 5 Has. The semiconductor layer 4 includes a CNT complex 7.

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

The structure of the semiconductor element is not limited to these. Further, the following description is common regardless of the structure of the semiconductor element unless otherwise specified.

(Base material)
The base material may be any material as long as at least the surface on which the electrode system is arranged has an insulating property. Examples of the base material include a base material made of an inorganic material such as a silicon wafer, glass, sapphire, and an alumina sintered body; polyimide, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyvinylidene fluoride, polysiloxane, and polyvinylphenol (PVP). , Polyester, Polycarbonate, Polysulfone, Polyethersulfone, Polyethylene, Polyphenylene sulfide, Polyparaxylene and other organic materials are preferred.

(electrode)
The material used for the gate electrode, the source electrode, and the drain electrode may be any conductive material that can be generally used as an electrode. For example, conductive metal oxides such as tin oxide, indium oxide, 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, and polysilicon and their alloys; inorganic conductive substances such as copper iodide and copper sulfide; polythiophene, polypyrrole, polyaniline; Complexes and the like; conductive polymers whose conductivity has been improved by doping with iodine and the like; carbon materials and the like; and materials containing organic components and conductors, etc., but are not limited thereto.

Above all, the electrode is made of an organic component and a conductor because the flexibility of the electrode is increased, the adhesion between the base material and the gate insulating layer is good even when the electrode is bent, and the electrical connection with the wiring and the semiconductor layer is good. It is preferable to contain it.

The conductor may be any conductive material that can be generally used as an electrode, but conductive particles are preferable.

Examples of the conductive particles include gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminum, tungsten, molybdenum and carbon. More preferred TEPCO commutators 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.

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

The method for forming the electrode is not particularly limited, and examples thereof include methods using known techniques such as resistance heating vapor deposition, electron beam beam, sputtering, plating, CVD, ion plating coating, inkjet, and printing. Further, as another example of the electrode forming method, a paste containing an organic component and a conductor is immersed in 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, and a dipping method. Examples thereof include a method of applying the paste onto an insulating substrate by a known technique such as a pulling method, and drying the paste using an oven, a hot plate, infrared rays, or the like to form the paste.

Further, as a method for forming the electrode pattern, the electrode thin film produced by the above method may be patterned into a desired shape by a known photolithography method or the like, or may be desired at the time of vapor deposition or sputtering of the electrode material. A pattern may be formed through a mask of the shape.

(Gate insulating layer)
The material used for the gate insulating layer is not particularly limited, but is an inorganic material such as silicon oxide and alumina; organic highs such as polyimide, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyvinylidene fluoride, polysiloxane, and polyvinylphenol (PVP). Molecular materials; or mixtures of inorganic material powders and organic materials can be mentioned.
Of these, those containing an organic compound containing a bond between silicon and carbon are preferable.

Examples of the organic compound containing a bond between silicon and carbon include a silane compound, an epoxy group-containing silane compound, a condensate thereof, or a polysiloxane containing these as a copolymerization component. Among these, polysiloxane is more preferable from the viewpoint of high insulating property and low-temperature curing.

The gate insulating layer may further contain a metal compound containing a bond between a metal atom and an oxygen atom, or a polymer in which inorganic particles are bonded.

The method for producing the gate insulating layer is not particularly limited, but for example, a method of applying a composition containing a material for forming an insulating layer to a substrate and drying the coating film to be heat-treated, if necessary. Can be mentioned. Examples of the coating method include known coating methods such as spin coating method, blade coating method, slit die coating method, screen printing method, bar coater method, mold method, printing transfer method, immersion pulling method, and inkjet method. The temperature of the heat treatment 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 from a plurality of insulating materials, or a plurality of insulating materials may be laminated to form a plurality of insulating layers.

(Semiconductor layer)
The semiconductor layer is formed by using the CNT dispersion liquid of the present invention, and contains a CNT composite in which a conjugated polymer having a side chain represented by the general formula (1) is attached to at least a part of the surface of the CNT. .. The semiconductor layer may further contain an organic semiconductor or an insulating material as long as it does not impair the electrical characteristics.

As a method for forming the semiconductor layer, a dry method such as resistance heating vapor deposition, electron beam, sputtering, or CVD can be used, but the coating method should be used from the viewpoint of manufacturing cost and compatibility with a large area. Is preferable. 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, a dipping pulling method, an inkjet method and the like can be preferably used. From these, it is preferable to select a coating method according to the coating film characteristics to be obtained, such as coating film thickness control and orientation control. Above all, for circuit formation, as described above, coating by inkjet is particularly preferable. Further, the formed coating film may be annealed in the atmosphere, under reduced pressure, or under the atmosphere of an inert gas such as nitrogen or argon.

(Second insulating layer)
The second insulating layer is formed on the side opposite to the gate insulating layer with respect to the semiconductor layer. The side opposite to the gate insulating layer 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, it is possible to adjust the characteristics of the semiconductor element and protect the semiconductor layer.

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 the gate electrode 2, a source electrode 5 and a drain electrode 6 provided on the gate electrode 2, and a semiconductor layer provided between the electrodes. It has 4 and a second insulating layer 8 that covers the semiconductor layer. The semiconductor layer 4 includes a CNT complex 7.

The material used for the second insulating layer is not particularly limited, but specifically, an inorganic material such as silicon oxide or alumina; polyimide or its derivative, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polyvinylidene fluoride, polyacrylonitrile. , Polysiloxane and its derivatives, polyvinylphenol and its derivatives, polynorbornene, polystyrene, polycarbonate and their derivatives, polyacrylic acid derivatives, polymethacrylic acid derivatives and other organic polymer materials; or inorganic material powders and organic polymer materials Examples thereof include a mixture or a mixture of an organic low molecular weight material and an organic high molecular weight material.

The second insulating layer contains electron-donating compounds such as amide compounds, imide compounds, urea compounds, amine compounds, imine compounds, aniline compounds, nitrile compounds, and alkylphosphine compounds. Is also good. Electron donation is the ability of one compound to donate electrons to another compound. An electron donating compound is a compound having an electron donating ability. By including such an electron-donating compound in the second insulating layer, a CNT-FET that normally exhibits p-type semiconductor characteristics can be converted into a semiconductor element that exhibits n-type semiconductor characteristics.

The method for forming the second insulating layer is not particularly limited, and methods such as resistance heating vapor deposition, electron beam beam, lamination, sputtering, and CVD can be used, but from the viewpoint of manufacturing cost and compatibility with a large area. It is preferable to use the coating method. The coating method includes at least a step of coating a composition in which a material for forming a second insulating layer is dissolved.

Further, the formed coating film may be subjected to an annealing treatment or hot air drying under an atmosphere, a reduced pressure, or an atmosphere of an inert gas such as nitrogen or argon.

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

μ = (δId / δVg) L · D / (W · εr · ε · Vsd) X10000 (a)
However, Id is the source-drain current (A), Vsd is the source-drain voltage (V), Vg is the gate voltage (V), D is the thickness of the gate insulating layer (m), and L is the channel length (m). W is the channel width (m), εr is the relative permittivity of the gate insulating layer, ε is the permittivity of the vacuum (8.85 × ^10-12 F / m), and δ is the amount of change in the corresponding physical quantity.

(Manufacturing method of semiconductor element)
The method for manufacturing a semiconductor device according to the embodiment of the present invention is not particularly limited, but preferably includes a step of forming a semiconductor layer by a coating method using the CNT dispersion liquid of the present invention. The method for forming the semiconductor layer is as described above, and the inkjet method is preferable as the coating method.

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

<Wireless communication device>
Next, a wireless communication device containing a semiconductor element formed by using the CNT dispersion liquid of the present invention will be described. This wireless communication device is a device that communicates information using wireless radio waves, such as a product tag, a shoplifting prevention tag, various tickets, and a smart card.

The wireless communication device includes at least the above-mentioned semiconductor element and an antenna. As a more specific configuration of the wireless communication device according to the embodiment of the present invention, for example, the one shown in FIG. 4 can be mentioned. This is sent from a power generation unit that rectifies an externally modulated wave signal received by the antenna 50 and supplies power to each unit, a demodulation circuit that demodulates the modulated wave signal and sends it to a control circuit, and a control circuit. It consists of a modulation circuit that modulates the data and sends it to the antenna, a control circuit that writes the demodulated data in the demodulation circuit to the storage circuit, and a control circuit that reads the data from the storage circuit and sends it to the modulation circuit. Each circuit unit is electrically connected. At least one or more of the power generation unit, the demodulation circuit, the control circuit, the modulation circuit, and the storage circuit includes the semiconductor element according to the embodiment of the present invention, and may further include a capacitor, a resistance element, and a diode. .. The storage circuit is further provided with a non-volatile storage unit such as a read-only storage unit in which information is written at the time of manufacture, an EEPROM (Electrically Erasable Programmable Read-Only Memory), and a FeRAM (Ferroelectric Random Access Memory). It may have a part. The power generation unit is composed of a capacitor and a diode.

The antenna, capacitor, resistance element, diode, and non-volatile rewritable storage unit may be any commonly used material, and the material and shape used are not particularly limited. Further, the material for electrically connecting each of the above 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 be electrically conductive. The width and thickness of the connection portion of each component are arbitrary.

The method for manufacturing the wireless communication device according to the embodiment of the present invention is not particularly limited, but may include a step of forming a semiconductor layer by a coating method using the CNT dispersion liquid of the present invention to form a semiconductor element. preferable. The method for forming the semiconductor element is as described above, and the inkjet method is preferable as the coating method.

<Product tag>
The use of the wireless communication device is not particularly limited, but can be applied to, for example, a product tag. As the product tag, a known one can be used, and examples thereof include a tag having a substrate and the wireless communication device coated with the substrate. When applied to a product tag having an identification information reply function, it is possible to identify a large number of products at the same time in a non-contact manner at a product checkout register. Therefore, it is possible to facilitate and speed up the payment process as compared with the identification by the barcode.

Further, for example, at the time of accounting for a product, the reader / writer can transmit the product information read from the product tag to a POS (Point of sale system) terminal. With this function, it is possible to register the sale of a product specified by the product information on the POS terminal, so that inventory management can be facilitated and speeded up.

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

<Solvent viscosity>
The viscosity of the solvent was measured using a viscometer (RE110L type manufactured by Toki Sangyo Co., Ltd.). When the measurement temperature is 25 ° C. and the viscosity of the solvent is 0.6 cP or more and 6 cP or less, the rotation speed is 100 rpm. The measurement was performed at several tens of rpm, and the average value of the results of the three measurements was taken as the viscosity of the solvent.

<Dispersibility of CNT>
The dispersibility of CNT was evaluated as follows. The CNT dispersion liquid is filtered with a membrane filter having a pore size of 10 μm, and the concentration reduction rate of the CNT dispersion liquid before and after filtration is A for 0% or more and 15% or less, B for more than 15% and 30% or less, and 50% or less for more than 30%. Was C, and D was greater than 50% and 100% or less.

<Inkjet coating property>
The inkjet coatability was evaluated as follows. Using an inkjet device (manufactured by Toray Engineering Co., Ltd.), the CNT dispersion liquid is discharged, the number of satellites is A for 0, B for 1-3, and C for 4 or more, and the coating position accuracy is within 20 μm. Was A, the case of more than 20 μm and less than 30 μm was B, the case of more than 30 μm and less than 50 μm was C, and the case of larger than 50 μm was D. For example, "coating position accuracy of 20 μm" means that the target pattern is coated with inkjet at 30 locations, the distance between the target landing position and the actual landing position is measured, and the average value is 20 μm. ..

<Mobility>
The mobility was evaluated as follows. A semiconductor element was manufactured using the CNT dispersion liquid, and the source-drain current (Id) -source-drain voltage (Vsd) characteristics of the semiconductor element were measured when the gate voltage (Vg) was changed. The semiconductor characteristic evaluation system 4200-SCS type (manufactured by Keithley Instruments Co., Ltd.) was used for the measurement, and the measurement was performed in the atmosphere. The mobility of the linear region was determined from the change in the value of Id at Vsd = + 5V when the value was changed from Vg = +30 to −30V.

<Example of preparation of CNT dispersion liquid>
Production Example 1 of CNT Dispersion Liquid; CNT Dispersion Liquid A
1.0 mg of CNT (manufactured by CNI, single-walled CNT, purity 95%) is added to a solution of 5.0 mg of the conjugated polymer represented by [10] in 10 mL of chloroform, and the ultrasonic homogenizer is cooled with ice. (VCX-500 manufactured by Tokyo Rika Kikai Co., Ltd.) was ultrasonically stirred at an output of 40% for 2 hours to obtain CNT dispersion solution 1 (CNT complex concentration 1.0 g / L with respect to solvent). Next, the CNT dispersion liquid 1 was filtered using a membrane filter (pore diameter 10 μm, diameter 25 mm, omnipore membrane manufactured by Millipore). After adding 5 mL of 1-methoxynaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) to the obtained filtrate, chloroform, which is a low boiling point solvent, was distilled off using a rotary evaporator to obtain a CNT dispersion liquid 2. .. 3 mL of 1-methoxynaphthalene was added to 1 mL of the CNT dispersion liquid 2 to obtain CNT dispersion liquid A (CNT complex concentration 0.03 g / L with respect to the solvent). The viscosity of the solvent was 5.8 cP.

Production Example 2 of CNT Dispersion Liquid; CNT Dispersion Liquid B
A CNT dispersion liquid B (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained in the same manner as in the above-mentioned preparation example of the CNT dispersion liquid A except that α-tetralone was used instead of 1-methoxynaphthalene. .. The viscosity of the solvent was 7.2 cP.

Production Example 3 of CNT Dispersion Liquid; CNT Dispersion Liquid C
The CNT dispersion liquid C is similar to the above-mentioned preparation example of the CNT dispersion liquid A, except that a mixed solvent of dimethyl phthalate / o-dichlorobenzene = 75% by weight / 25% by weight is used instead of 1-methoxynaphthalene. (Concentration of CNT complex with respect to solvent 0.03 g / L) was obtained. The viscosity of the solvent was 7.8 cP.

Production Example 4 of CNT Dispersion Liquid; CNT Dispersion Liquid D
CNT dispersion in the same manner as in the above-mentioned preparation example of CNT dispersion liquid A, except that a mixed solvent of ethylene glycol monophenyl ether / o-dichlorobenzene = 75% by weight / 25% by weight was used instead of 1-methoxynaphthalene. Liquid D (CNT complex concentration 0.03 g / L with respect to solvent) was obtained. The viscosity of the solvent was 8.5 cP.

Production Example 5 of CNT Dispersion Liquid; CNT Dispersion Liquid E
CNT dispersion in the same manner as in the above-mentioned preparation example of CNT dispersion liquid A, except that a mixed solvent of propylene glycol monophenyl ether / o-dichlorobenzene = 75% by weight / 25% by weight was used instead of 1-methoxynaphthalene. Liquid E (CNT complex concentration 0.03 g / L with respect to solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 6 of CNT Dispersion Liquid; CNT Dispersion Liquid F
The CNT dispersion liquid F is similar to the above-mentioned preparation example of the CNT dispersion liquid A, except that a mixed solvent of phenyldiglycol / o-dichlorobenzene = 75% by weight / 25% by weight is used instead of 1-methoxynaphthalene. (Concentration of CNT complex with respect to solvent 0.03 g / L) was obtained. The viscosity of the solvent was 12.8 cP.

Production Example 7 of CNT Dispersion Liquid; CNT Dispersion Liquid G
The CNT dispersion liquid G was similar to the above-mentioned preparation example of the CNT dispersion liquid A, except that a mixed solvent of phenyldiglycol / o-dichlorobenzene = 83% by weight / 17% by weight was used instead of 1-methoxynaphthalene. (Concentration of CNT complex with respect to solvent 0.03 g / L) was obtained. The viscosity of the solvent was 15.5 cP.

Production Example 8 of CNT Dispersion Liquid; CNT Dispersion Liquid H
The CNT dispersion liquid H is similar to the above-mentioned preparation example of the CNT dispersion liquid A, except that a mixed solvent of phenyldiglycol / o-dichlorobenzene = 90% by weight / 10% by weight is used instead of 1-methoxynaphthalene. (Concentration of CNT complex with respect to solvent 0.03 g / L) was obtained. The viscosity of the solvent was 21.8 cP.

Preparation Example 9 of CNT Dispersion Liquid; CNT Dispersion Liquid I
CNT dispersion I (solvent) was used in the same manner as in the above-mentioned preparation example of CNT dispersion A, except that a mixed solvent of terpineol / o-dichlorobenzene = 75% by weight / 25% by weight was used instead of 1-methoxynaphthalene. The CNT complex concentration was 0.03 g / L). The viscosity of the solvent was 8.9 cP.

Preparation Example 10 of CNT Dispersion Liquid; CNT Dispersion Liquid J
CNT dispersion J (solvent) was used in the same manner as in the above-mentioned preparation example of CNT dispersion A, except that a mixed solvent of terpineol / 1-chloronaphthalene = 95% by weight / 5% by weight was used instead of 1-methoxynaphthalene. The CNT complex concentration was 0.03 g / L). The viscosity of the solvent was 34.9 cP.

Preparation Example 11 of CNT Dispersion Liquid; CNT Dispersion Liquid K
Similar to the production example of the CNT dispersion liquid E, CNTs are used in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by the above [1] is used instead of the conjugated polymer represented by the above [10]. Dispersion K (CNT complex concentration 0.03 g / L with respect to solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Preparation Example 12 of CNT Dispersion Liquid; CNT Dispersion Liquid L
CNTs are produced in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by the above [2] is used instead of the conjugated polymer represented by the above [10]. A dispersion L (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 13 of CNT Dispersion Liquid; CNT Dispersion Liquid M
CNTs are produced in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by the above [3] is used instead of the conjugated polymer represented by the above [10]. A dispersion M (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Preparation Example 14 of CNT Dispersion Liquid; CNT Dispersion Liquid N
Similar to the production example of the CNT dispersion liquid E, CNTs are used in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by the above [4] is used instead of the conjugated polymer represented by the above [10]. A dispersion N (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Preparation Example 15 of CNT Dispersion Liquid; CNT Dispersion Liquid O
Similar to the production example of the CNT dispersion liquid E, CNTs are used in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by the above [5] is used instead of the conjugated polymer represented by the above [10]. The dispersion O (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 16 of CNT Dispersion Liquid; CNT Dispersion Liquid P
CNTs are produced in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by [6] is used instead of the conjugated polymer represented by [10]. The dispersion P (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 17 of CNT Dispersion Liquid; CNT Dispersion Liquid Q
CNTs are produced in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by the above [8] is used instead of the conjugated polymer represented by the above [10]. The dispersion Q (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 18 of CNT Dispersion Liquid; CNT Dispersion Liquid R
Similar to the production example of the CNT dispersion liquid E, CNTs are used in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by the above [9] is used instead of the conjugated polymer represented by the above [10]. A dispersion R (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 19 of CNT Dispersion Liquid; CNT Dispersion Liquid S
CNTs are produced in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by [13] is used instead of the conjugated polymer represented by [10]. The dispersion S (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 20 of CNT Dispersion Liquid; CNT Dispersion Liquid T
CNTs are produced in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by [12] is used instead of the conjugated polymer represented by [10]. The dispersion T (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 21 of CNT Dispersion Liquid; CNT Dispersion Liquid U
CNTs are produced in the same manner as in the production example of the CNT dispersion liquid E, except that the conjugated polymer represented by [14] is used instead of the conjugated polymer represented by [10]. A dispersion U (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained. The viscosity of the solvent was 9.6 cP.

Production Example 22 of CNT Dispersion Liquid; CNT Dispersion Liquid V
Preparation of the CNT dispersion liquid A except that poly-3-hexylthiophene was used instead of the conjugated polymer represented by [10] and o-dichlorobenzene was used instead of 1-methoxynaphthalene. In the same manner as in the example, CNT dispersion V (concentration of CNT complex with respect to solvent 0.03 g / L) was obtained. The viscosity of the solvent was 1.3 cP.

Production Example 23 of CNT Dispersion Liquid; CNT Dispersion Liquid W
The CNT dispersion liquid W (CNT complex concentration 0.03 g / L with respect to the solvent) was obtained in the same manner as in the above-mentioned preparation example of the CNT dispersion liquid V except that α-tetralone was used instead of o-dichlorobenzene. .. The viscosity of the solvent was 7.2 cP.

Preparation Example 24 of CNT Dispersion Liquid; CNT Dispersion Liquid X
CNT dispersion liquid X (concentration of CNT complex with respect to solvent 0. 03 g / L) was obtained. The viscosity of the solvent was 2.0 cP.

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

10 g of the obtained polysiloxane solution A and aluminum bis (ethylacetacetate) mono (2,4-pentanionate) (trade name "Aluminum chelate D", manufactured by Kawaken Fine Chemical Co., Ltd., hereinafter referred to as aluminum chelate D) 13 0.0 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 polysiloxane in this solution was 20 parts by weight with respect to 100 parts by weight of aluminum chelate D.

<Example of manufacturing a semiconductor device>
Fabrication Example 1 of Semiconductor Device
The semiconductor device shown in FIG. 1 was manufactured. A gate electrode 2 was formed by vacuum-depositing chromium with a thickness of 5 nm and gold with a thickness of 50 nm on a glass substrate 1 (thickness 0.7 mm) through a mask by a resistance heating method. Next, the gate insulating layer solution A was spin-coated on the substrate (2000 rpm × 30 seconds) and heat-treated at 200 ° C. for 1 hour under a nitrogen stream to form a gate insulating layer 3 having a film thickness of 600 nm. Next, gold was vacuum-deposited to a thickness of 50 nm through a mask by a resistance heating method to form a source electrode 5 and a drain electrode 6. Next, a CNT dispersion liquid was inkjet-coated between the source electrode 5 and the drain electrode 6 and heat-treated at 180 ° C. for 30 minutes under a nitrogen stream to form the semiconductor layer 4. In this way, a semiconductor element was obtained. The width (channel width) of the source / drain electrodes of this semiconductor element was set to 200 μm, and the distance between the source / drain electrodes (channel length) was set to 20 μm.

<Example>
Example 1
Using the CNT dispersion liquid A, the CNT dispersibility and the inkjet coating property were evaluated. The CNT dispersibility was C, the inkjet coating property was satellite B, and the coating position accuracy was B. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.61 cm ² / V · s.

Example 2
Using the CNT dispersion liquid B, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was C, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.65 cm ² / V · s.

Example 3
Using the CNT dispersion liquid C, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.87 cm ² / V · s.

Example 4
Using the CNT dispersion liquid D, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.90 cm ² / V · s.

Example 5
Using the CNT dispersion liquid E, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.88 cm ² / V · s.

Example 6
Using the CNT dispersion liquid F, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.89 cm ² / V · s.

Example 7
Using the CNT dispersion liquid G, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was B. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.80 cm ² / V · s.

Example 8
Using the CNT dispersion liquid H, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was C. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.74 cm ² / V · s.

Example 9
Using the CNT dispersion liquid I, the CNT dispersibility and the inkjet coating property were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.85 cm ² / V · s.

Example 10
Using the CNT dispersion liquid J, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was C. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.72 cm ² / V · s.

Example 11
Using the CNT dispersion liquid K, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.88 cm ² / V · s.

Example 12
Using the CNT dispersion liquid L, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.91 cm ² / V · s.

Example 13
Using the CNT dispersion liquid M, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.93 cm ² / V · s.

Example 14
Using the CNT dispersion liquid N, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was A, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 1.2 cm ² / V · s.

Example 15
Using the CNT dispersion liquid O, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.90 cm ² / V · s.

Example 16
Using the CNT dispersion liquid P, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was A, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 1.1 cm ² / V · s.

Example 17
Using the CNT dispersion liquid Q, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was B, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.89 cm ² / V · s.

Example 18
Using the CNT dispersion liquid R, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was A, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 1.2 cm ² / V · s.

Example 19
Using the CNT dispersion liquid S, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was A, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 1.4 cm ² / V · s.

Example 20
Using the CNT dispersion liquid T, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was A, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 1.2 cm ² / V · s.

Example 21
Using the CNT dispersion liquid U, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was A, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 1.4 cm ² / V · s.

Comparative Example 1
Using the CNT dispersion liquid V, the CNT dispersibility and the inkjet coating property were evaluated. The CNT dispersibility was A, the inkjet coating property was satellite C, and the coating position accuracy was D. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.25 cm ² / V · s.

Comparative Example 2
Using the CNT dispersion liquid W, the CNT dispersibility and the inkjet coatability were evaluated. The CNT dispersibility was D, the inkjet coating property was satellite A, and the coating position accuracy was A. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.30 cm ² / V · s.

Comparative Example 3
Using the CNT dispersion liquid X, the CNT dispersibility and the inkjet coating property were evaluated. The CNT dispersibility was D, the inkjet coating property was satellite C, and the coating position accuracy was C. Further, the semiconductor element was manufactured in the same manner as in Production Example 1 of the semiconductor device. The mobility was 0.19 cm ² / V · s.

The results of each example and comparative example are summarized in Tables 1 to 4.

1 Base material 2 Gate electrode 3 Gate insulating layer 4 Semiconductor layer 5 Source electrode 6 Drain electrode 7 CNT composite 8 Second insulating layer 50 Antenna

Claims (9)

A carbon nanotube complex in which a conjugated polymer is attached to at least a part of the surface of the carbon nanotube,
A carbon nanotube dispersion liquid containing at least a solvent,
The conjugated polymer has a side chain represented by the general formula (1) and has a side chain.
The solvent is a single or mixed solvent
The single or mixed solvent has a viscosity of 7 to 13 cP and
A carbon nanotube dispersion liquid, wherein the single or mixed solvent contains a solvent having a boiling point of 150 to 290 ° C. or a solvent having a vapor pressure of 0.9 to 500 Pa.

(In the general formula (1), R ¹ represents an alkylene group or a cycloalkylene group. X represents a single bond, an alkenylene group, an alkynylene group, an arylene group or a heteroarylene group. A represents a hydroxy group or an alkylsulfanyl. A group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an N-alkylcarbonylamino group, an N-alkyl-N-alkylcarbonylamino group, or a group represented by the general formula (2). Show.)

(In the general formula (2), R ² represents an alkylene group. R ³ represents a hydrogen atom or a hydroxy group. M represents an integer of 1 or more.) A carbon nanotube complex in which a conjugated polymer is attached to at least a part of the surface of the carbon nanotube,
A carbon nanotube dispersion liquid containing at least a solvent,
The conjugated polymer has a side chain represented by the general formula (1) and has a side chain.
The solvent is a single or mixed solvent
The single or mixed solvent has a viscosity of 5-40 cP and
The single or mixed solvent contains a solvent having a boiling point of 150 to 290 ° C. or a solvent having a vapor pressure of 0.9 to 500 Pa.
A carbon nanotube dispersion liquid, wherein the single or mixed solvent contains a halogen-based aromatic solvent in an amount of 5% by weight or more in the total solvent.

(In general formula (1), R ¹ Indicates an alkylene group or a cycloalkylene group. X represents a single bond, an alkenylene group, an alkynylene group, an arylene group or a heteroarylene group. A is a hydroxy group, an alkylsulfanyl group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an N-alkylcarbonylamino group, an N-alkyl-N-alkylcarbonylamino group, or a general formula ( The group represented by 2) is shown. )

(In general formula (2), R ² Indicates an alkylene group. R ³ Indicates a hydrogen atom or a hydroxy group. m represents an integer of 1 or more. ) A carbon nanotube complex in which a conjugated polymer is attached to at least a part of the surface of the carbon nanotube,
A carbon nanotube dispersion liquid containing at least a solvent,
The conjugated polymer has a side chain represented by the general formula (1) and has a side chain.
The solvent is a single or mixed solvent
The single or mixed solvent has a viscosity of 5-40 cP and
The single or mixed solvent contains a solvent having a boiling point of 150 to 290 ° C. or a solvent having a vapor pressure of 0.9 to 500 Pa.
A carbon nanotube dispersion liquid, wherein the mixed solvent contains a halogen-based aromatic solvent in an amount of 5% by weight or more and 50% by weight or less in the total solvent .

(In the general formula (1), R ¹ represents an alkylene group or a cycloalkylene group. X represents a single bond, an alkenylene group, an alkynylene group, an arylene group or a heteroarylene group. A represents a hydroxy group or an alkylsulfanyl. A group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an N-alkylcarbonylamino group, an N-alkyl-N-alkylcarbonylamino group, or a group represented by the general formula (2). Show.)

(In the general formula (2), R ² represents an alkylene group. R ³ represents a hydrogen atom or a hydroxy group . M represents an integer of 1 or more.) A carbon nanotube complex in which a conjugated polymer is attached to at least a part of the surface of the carbon nanotube,
A carbon nanotube dispersion liquid containing at least a solvent,
The conjugated polymer has a side chain represented by the general formula (1) and has a side chain.
The solvent is a single or mixed solvent
The single or mixed solvent has a viscosity of 5-40 cP and
The single or mixed solvent contains a solvent having a boiling point of 150 to 290 ° C. or a solvent having a vapor pressure of 0.9 to 500 Pa.
A carbon nanotube dispersion liquid, wherein the mixed solvent contains a halogen-based aromatic solvent in an amount of 15% by weight or more and 35% by weight or less in the total solvent.

(In the general formula (1), R ¹ represents an alkylene group or a cycloalkylene group. X represents a single bond, an alkenylene group, an alkynylene group, an arylene group or a heteroarylene group. A represents a hydroxy group or an alkylsulfanyl. A group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an N-alkylcarbonylamino group, an N-alkyl-N-alkylcarbonylamino group, or a group represented by the general formula (2). Show.)

(In the general formula (2), R ² represents an alkylene group. R ³ represents a hydrogen atom or a hydroxy group . M represents an integer of 1 or more.) The carbon nanotube dispersion liquid according to any one of claims 2 to 4, wherein the single or mixed solvent has a viscosity of 5 to 20 cP. A is an alkylsulfonyl group, a dialkylaminocarbonyl group, an N-alkyl-N-alkylcarbonylamino group, or a group represented by the general formula (2), in which m is represented by an integer of 2 or more. The carbon nanotube dispersion liquid according to any one of claims 1 to 5. A method for manufacturing a semiconductor device, comprising 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 a gate insulating layer that insulates the semiconductor layer from the gate electrode. A method for manufacturing a semiconductor device, which comprises a step of forming the semiconductor layer by a coating method using the carbon nanotube dispersion liquid according to any one of claims 1 to 6. The method for manufacturing a semiconductor device according to claim 7 , wherein the coating method is an inkjet method. A semiconductor device including 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 a gate insulating layer that insulates the semiconductor layer from the gate electrode, and an antenna. A method for manufacturing a wireless communication device, comprising the step of forming the semiconductor element by the method according to claim 7 or 8.

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