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WO2023033465A1 - Transistor ntc utilisant une réaction click et son procédé de fabrication - Google Patents

Transistor ntc utilisant une réaction click et son procédé de fabrication Download PDF

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Publication number
WO2023033465A1
WO2023033465A1 PCT/KR2022/012825 KR2022012825W WO2023033465A1 WO 2023033465 A1 WO2023033465 A1 WO 2023033465A1 KR 2022012825 W KR2022012825 W KR 2022012825W WO 2023033465 A1 WO2023033465 A1 WO 2023033465A1
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polymer
formula
cnt
substrate
functional group
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Korean (ko)
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임보규
박종목
정서현
공호열
정유진
김예진
이승훈
기르마헤녹
윤수열
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Korea Research Institute of Chemical Technology KRICT
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  • the present invention relates to a CNT film using a click reaction and a transistor including the same, and specifically, by using a CNT film having excellent stability to water or organic solvents and easily adjusting density through a click reaction, high reliability between devices It relates to a method of manufacturing a field effect transistor (FET) having a.
  • FET field effect transistor
  • a CNT transistor in order to manufacture a CNT transistor, there are methods of immersing the entire substrate in a CNT solution, spin-coating the CNT solution on a substrate layer, or directly patterning a carbon nanotube material on a substrate using a printing process.
  • all of the above methods have a problem in that the bonding strength between the substrate and the CNT is insufficient, so that they are easily peeled off by the organic solvent during the washing process.
  • the CNT film manufacturing method which is generally formed through a random network, has non-uniform connectivity between CNTs in the film, resulting in a decrease in reliability between manufactured devices.
  • the present invention has excellent stability to water or organic solvents through CNT growth immobilized on a substrate using a click reaction, and realizes high CNT density between films by adjusting the CNT density through click reactivity control. Through this, a transistor having high reliability is provided.
  • the present invention provides a method for manufacturing a high-density CNT transistor with a relatively easy process using a click reaction.
  • the inventors of the present inventors have made continuous research to develop a CNT transistor and a method for manufacturing the same, which have good adhesion between the CNT film and the substrate, excellent stability to water or organic solvents, and high reliability between devices.
  • a CNT transistor is manufactured using a click reaction, a CNT film is uniformly formed at a high density, has excellent stability to water or organic solvents, does not peel off even after washing, and can manufacture a CNT transistor with excellent device-to-device reliability. It was discovered that it could be done, and the present invention was completed.
  • the present invention is a polymer layer formed from a first polymer on a substrate; a composite layer formed from a second polymer-CNT composite on the polymer layer; and a metal electrode formed on the composite layer, wherein the second polymer-CNT composite is a CNT lapped by the second polymer, and the polymer layer and the composite layer are connected through triazole.
  • the triazole may be represented by Chemical Formula 1 below.
  • the first polymer is represented by Formula 2 below
  • the second polymer is represented by Formula 3 below
  • the triazole is a click of the first polymer and the second polymer. It is formed by a reaction, and the click reaction can be represented by Reaction Formula 1 below.
  • P 1 is a residue derived from the first polymer
  • P 2 is a residue derived from the second polymer
  • P 2 (CNT) is a residue derived from the second polymer-CNT complex
  • FG 1 is an alkynyl functional group
  • FG 2 is an azide functional group
  • x and y are integers greater than or equal to 1;
  • the first polymer may be an acrylic copolymer.
  • Chemical Formula 2 may be represented by Chemical Formula 4 or Chemical Formula 5 below.
  • FG 1 is an alkynyl functional group
  • FG 3 is an epoxy functional group
  • p 1 to p 2 are repeating units derived from monomers having FG 1 functional groups at their ends;
  • p 3 is a repeating unit derived from a monomer having an FG 3 functional group at the terminal;
  • z, k and t are integers from 1 to 7;
  • a, b and c are integers greater than or equal to 1.
  • Chemical Formula 4 may be represented by Chemical Formula 6 below.
  • Ar is a trivalent aromatic radical
  • R 1 to R 2 are independently C 1-50 alkylene, C 3-50 cycloalkylene, C 6-50 arylene, C 3-50 heteroarylene, C 1-50 alkoxycarbonylene or combinations thereof; ;
  • alkylene, cycloalkylene, arylene, heteroarylene and alkoxycarbonylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C 1-20 alkyl, C 2-20 alkyl kenyl, C 2-20 alkynyl, C 1-20 haloalkyl, C 1-20 alkoxy, C 1-20 alkoxycarbonyl, C 3-30 cycloalkyl, (C 6-30 )ar(C 1-20 ) It may be substituted with one or more selected from alkyl, C 6-30 aryl and C 3-30 heteroaryl;
  • FG 1 is an alkynyl functional group
  • z and k are integers from 1 to 7;
  • a and b are integers greater than or equal to 1.
  • Chemical Formula 6 may be represented by Chemical Formula 7 below.
  • R 2 to R 3 are independently C 1-10 alkylene
  • a and b are integers greater than or equal to 1.
  • Chemical Formula 5 may be represented by Chemical Formula 8 below.
  • Ar is a trivalent aromatic radical
  • R 1 , R 2 and R 4 are independently C 1-50 alkylene, C 3-50 cycloalkylene, C 6-50 arylene, C 3-50 heteroarylene, C 1-50 alkoxycarbonylene or these is a combination of;
  • alkylene, cycloalkylene, arylene, heteroarylene and alkoxycarbonylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C 1-20 alkyl, C 2-20 alkyl kenyl, C 2-20 alkynyl, C 1-20 haloalkyl, C 1-20 alkoxy, C 1-20 alkoxycarbonyl, C 3-30 cycloalkyl, (C 6-30 )ar(C 1-20 ) It may be substituted with one or more selected from alkyl, C 6-30 aryl and C 3-30 heteroaryl;
  • R 5 is hydrogen or C 1-3 alkyl
  • FG 1 is an alkynyl functional group
  • FG 3 is an epoxy functional group
  • z, k and t are integers from 1 to 7;
  • a, b and c are integers greater than or equal to 1.
  • Chemical Formula 8 may be represented by Chemical Formula 9 below.
  • R 2 to R 4 are independently C 1-10 alkylene
  • R 5 is hydrogen or methyl
  • a, b and c are integers greater than or equal to 1.
  • the second polymer may be a fluorene-based copolymer.
  • Chemical Formula 3 may be a copolymer including a repeating unit (n) of Chemical Formula 10 and a repeating unit (m) of Chemical Formula 11 below.
  • R 6 to R 7 are independently C 5-50 alkylene
  • R 8 to R 9 are independently C 5-50 alkyl.
  • the CNT transistor may further include a self-assembled monolayer (SAM) between the substrate and the polymer layer.
  • SAM self-assembled monolayer
  • the self-assembled monolayer may be formed of a compound represented by Chemical Formula 12 below.
  • R 10 is C 1-10 alkylene
  • R 11 to R 13 are independently hydroxy, halogen, C 1-10 alkyl, C 1-10 haloalkyl, C 1-10 alkoxy or C 1-10 alkoxycarbonyl.
  • the CNT in the second polymer-CNT composite, may be a semiconducting single-walled carbon nanotube (sc-SWCNT).
  • sc-SWCNT semiconducting single-walled carbon nanotube
  • the present invention is a polymer layer formed from a first polymer on a substrate; a composite layer formed from a second polymer-CNT composite on the polymer layer; and a metal electrode formed on the composite layer, wherein the second polymer-CNT composite is a CNT lapped by the second polymer, and the polymer layer and the composite layer are connected through triazole.
  • a manufacturing method can be provided.
  • the method of manufacturing the CNT transistor in the method of manufacturing a transistor according to an embodiment of the present invention, the method of manufacturing the CNT transistor
  • (d) forming a source electrode and a drain electrode on the composite layer may include.
  • step (a) In the method for manufacturing a transistor according to an embodiment of the present invention, in the step (a),
  • the first polymer in step (a-3), may be represented by Chemical Formula 4 below.
  • FG 1 is an alkynyl functional group
  • p 1 to p 2 are repeating units derived from monomers having FG 1 functional groups at their ends;
  • z and k are integers from 1 to 7;
  • a and b are integers greater than or equal to 1.
  • the step (a-4) may further include a pattern forming step.
  • step (a) In the method for manufacturing a transistor according to an embodiment of the present invention, the step (a)
  • (a'-4) washing the unfixed compound on the substrate with a solvent may include.
  • the first polymer in the step (a'-2), may be represented by Chemical Formula 5 below.
  • FG 1 is an alkynyl functional group
  • FG 3 is an epoxy functional group
  • p 1 to p 2 are repeating units derived from monomers having FG 1 functional groups at their ends;
  • p 3 is a repeating unit derived from a monomer having an FG 3 functional group at the terminal;
  • z, k and t are integers from 1 to 7;
  • a, b and c are integers greater than or equal to 1.
  • the second polymer-CNT composite solution may include a second polymer, CNT, and a solvent.
  • the CNT transistor according to the present invention can have high stability against water or organic solvents since a CNT film is uniformly formed at a high density using a click reaction.
  • conventional CNT transistors manufactured by spray coating and spin coating CNT solutions have large differences in physical properties between devices, reproducibility and reliability cannot be secured, whereas the CNT transistor according to the present invention achieves high reproducibility and reliability with a relatively simple method.
  • a CNT film having a desired density can be manufactured by controlling the time of the click reaction, and a transistor coated with CNTs can be obtained with a high density with a short reaction time, thereby reducing the manufacturing process. It has the advantage of being simple.
  • the CNT transistor according to the present invention has excellent adhesion to substrates, high density, uniformity, high stability to water or organic solvents, high reproducibility and ease of processing, and thus various conductivity such as semiconductor devices, displays, transparent electrodes and biosensors. It can be applied as a composite material.
  • Example 1 is a schematic diagram showing a simple method of manufacturing a transistor of Example 1;
  • Example 2 is a photograph showing a shadow mask used in Example 1 and a CNT transistor device according to Example 1;
  • Figure 3 (a) is the result of ultraviolet-visible spectroscopy (UV-Vis spectroscopy) before and after washing with a solvent after UV curing of the acrylate copolymer (i) solution coated in Example 1 according to the present invention Is a graph showing, (b) is a graph showing the results of UV-visible spectroscopy before and after washing with a solvent after thermally curing the acrylate copolymer (ii) solution coated in Example 3 according to the present invention.
  • UV-Vis spectroscopy ultraviolet-visible spectroscopy
  • 5 is a graph showing electrical characteristic curves (output curve and transfer curve) of all elements of the CNT transistor according to Examples 3 to 4;
  • FIG. 6 is a graph showing electrical characteristic curves (output curve and transfer curve) of all elements of a CNT transistor according to Comparative Example 1.
  • weight% or ratio means weight% or weight ratio, and unless otherwise defined, weight% is any one component of the entire composition It means the weight percent occupied in the composition.
  • numerical ranges include lower and upper limits and all values within that range, increments logically derived from the shape and breadth of the defined range, all values defined therebetween, and the upper limit of the numerical range defined in a different form. and all possible combinations of lower bounds. Unless otherwise specifically defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.
  • a layer when a layer is said to be located “on” another layer in the present invention, this includes not only the case where a certain layer is in contact with another layer, but also the case where one or more other layers exist between two layers.
  • polymer used herein includes polymers and copolymers.
  • copolymer generally means any polymer derived from more than one species of monomer, where the polymer comprises corresponding repeat units of more than one species.
  • a copolymer is a reaction product of two or more types of monomers, and thus may include two or more types of corresponding repeating units.
  • Copolymers can exist as block copolymers, random copolymers and/or alternating copolymers.
  • acrylic used herein includes both methacrylic and acrylic.
  • acrylate used herein includes both methacrylate and acrylate.
  • residue refers to a portion of a polymer excluding a specific functional group, and the type of the polymer is not particularly limited.
  • wrapping in this specification means that a hydrocarbon chain wraps a CNT by electrostatic interaction, and may also include meanings of coating, coating, bonding, and attachment.
  • the electrostatic interaction may mean a ⁇ - ⁇ stacking interaction.
  • alkyl as used herein includes both straight-chain and branched chains, and may have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • halogen and “halo” herein refer to fluorine, chlorine, bromine or iodine.
  • haloalkyl refers to an alkyl group in which one or more hydrogen atoms are substituted with halogen atoms.
  • haloalkyl is -CF 3 , -CHF 2 , -CH 2 F, -CBr 3 , -CHBr 2 , -CH 2 Br, -CC1 3 , -CHC1 2 , -CH 2 CI, -CI 3 , -CHI 2 , -CH 2 I, -CH 2 -CF 3 , -CH 2 -CHF 2 , -CH 2 -CH 2 F, -CH 2 -CBr 3 , -CH 2 -CHBr 2 , -CH 2 -CH 2 Br, -CH 2 -CC1 3 , -CH 2 -CHC1 2 , -CH 2 -CH 2 CI, -CH 2 -CI 3 , -CH 2 -CHI 2 , -CH
  • alkenyl as used herein means a saturated straight-chain or branched hydrocarbon containing 2 to 30, preferably 2 to 20, carbon atoms and at least one carbon-carbon double bond.
  • alkynyl as used herein means a saturated straight-chain or branched hydrocarbon containing 2 to 30, preferably 2 to 20, carbon atoms and at least one carbon-carbon triple bond.
  • alkoxy as used herein means -OCH 3 , -OCH 2 CH 3 , -O(CH 2 ) 2 CH 3 , -O(CH 2 ) 3 CH 3 , -O(CH 2 ) 4 CH 3 , -O (CH 2 ) 5 CH 3 , and the like, wherein alkyl is as defined above.
  • alkoxycarbonyl radicals include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, and the like, but Not limited.
  • cycloalkyl refers to a monocyclic or polycyclic saturated ring having carbon and hydrogen atoms and having no carbon-carbon multiple bonds.
  • cycloalkyl groups include, but are not limited to, C 3-10 cycloalkyl (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl).
  • a cycloalkyl group may be optionally substituted.
  • a cycloalkyl group is a monocyclic or bicyclic ring (ring).
  • aralkyl refers to substitution of one or more hydrogens of alkyl with aryl, and includes benzyl and the like.
  • alkylene alkenylene, alkynylene, cycloalkylene,” “arylene,” “heteroarylene,” and “alkoxycarbonylene” as used herein refer to “alkyl,” “alkenyl,” respectively.
  • alkynyl means a divalent organic radical derived by the removal of one hydrogen from “cycloalkyl”, “aryl”, “heteroaryl” and “alkoxycarbonyl”, wherein said alkyl, alkenyl, alkynyl, cyclo followss the respective definitions of alkyl, aryl, heteroaryl and alkoxycarbonyl.
  • hydroxy as used herein means -OH, "nitro” means -NO 2 , "cyano” means -CN, "amino” means -NH 2 , and ""Carboxyl” means -COOH, and “carboxylate” means -COOM.
  • the M may be an alkali metal or an earth metal.
  • alkali metal refers to chemical elements other than hydrogen in Group 1 of the periodic table, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
  • alkaline earth metal refers to beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra), which are elements of Group 2 of the periodic table.
  • the present invention provides a CNT transistor including a polymer layer formed from a first polymer on a substrate, a composite layer formed from a second polymer-CNT composite on the polymer layer, and a metal electrode formed on the composite layer.
  • the second polymer-CNT composite may be one in which CNTs are wrapped by the second polymer, and the polymer layer and the composite layer may be connected through triazole.
  • the substrate may be an inorganic substrate including glass, quartz and silicon or polyethylene terephthalate, polyethylene sulfone, polycarbonate, polystyrene, polypropylene, polyester, polyimide, polyetheretherketone, polyetherimide, acrylic resin and olefin male. It may be an organic substrate including a mid copolymer or the like, but is not limited thereto.
  • the substrate may be a conventional silicon wafer or a substrate in which an oxide film is formed on the inorganic substrate, and may be a flexible substrate including the organic substrate and plastic, but if a CNT film can be formed on the substrate, it is particularly limited It doesn't work. Additionally, physical and chemical treatment may be performed to improve adhesion between the substrate and the CNT film. By forming a CNT film on the substrate, it can be applied to semiconductor devices, transparent electrodes and displays.
  • the triazole may be represented by Chemical Formula 1 below.
  • the first polymer is represented by Formula 2 below
  • the second polymer is represented by Formula 3 below
  • the triazole is a click of the first polymer and the second polymer. It is formed by a reaction, and the click reaction can be represented by Reaction Formula 1 below.
  • P 1 is a residue derived from the first polymer
  • P 2 is a residue derived from the second polymer
  • P 2 (CNT) is a residue derived from the second polymer-CNT complex.
  • FG 1 is an alkynyl functional group
  • FG 2 is an azide functional group
  • x and y are integers greater than or equal to 1.
  • the residue derived from the first polymer refers to a portion of the first polymer excluding the FG 1 functional group, and the first polymer is the same as described below.
  • the residue derived from the second polymer refers to the remainder of the second polymer except for the FG 2 functional group, and the second polymer is the same as described below.
  • the residue derived from the second polymer-CNT composite refers to the remainder of the second polymer-CNT composite except for the FG 2 functional group, and the second polymer-CNT composite is the same as described below.
  • Reaction Scheme 1 may be specifically expressed as Reaction Scheme 2 below.
  • the alkynyl functional group of Chemical Formula 2 and the azide functional group of Chemical Formula 3 may form a triazole ring through a click reaction in the presence of a copper catalyst.
  • a polymer layer and a composite layer may be formed on the substrate.
  • the type of the first polymer is not particularly limited as long as it has an alkynyl functional group
  • the type of the second polymer is not particularly limited as long as it has an azide functional group.
  • the first polymer is not particularly limited in kind as long as it has a hydroxyl, epoxy, carboxyl, thiol, alkene and alkynyl, preferably epoxy and alkynyl functional group on its side chain.
  • the first polymer may be an acrylic copolymer, and the acrylic copolymer may be obtained by polymerizing two or more types of monomers, and the monomer may be an acrylic monomer or a methacrylic monomer.
  • the monomers may have hydroxyl, epoxy, carboxyl, thiol, alkene, and alkynyl functional groups at terminal ends, and may preferably have epoxy and alkynyl functional groups.
  • the monomers may be directly synthesized and used, or commercially available products may be used, but are not limited thereto.
  • the acrylic copolymer may be synthesized by a commonly used polymerization method. It may preferably be solution polymerization, but is not limited thereto.
  • the solution polymerization may be polymerization including the monomer, initiator and solvent, and the initiator and solvent are not particularly limited as long as they are commonly used, but preferably, azobisisobutyronitrile (AIBN) can be used as the initiator. and the solvent may be dimethylformamide (DMF).
  • AIBN azobisisobutyronitrile
  • DMF dimethylformamide
  • the content is not particularly limited as long as the physical properties described in the present invention are not impaired.
  • the first polymer may have a number average molecular weight (Mn) of 5,000 to 100,000 Da, preferably 10,000 to 60,000 Da, and more preferably 10,000 to 30,000 Da, but is not limited thereto.
  • Mn number average molecular weight
  • the number average molecular weight may be adjusted according to the input ratio of the monomers and polymerization conditions.
  • Formula 2 may be represented by Formula 4 or Formula 5 below.
  • FG 1 is an alkynyl functional group
  • p 1 to p 2 are repeating units derived from a monomer having an FG 1 functional group at the ends
  • z and k are independently integers from 1 to 7, and a
  • b is an integer greater than or equal to 1;
  • z and k may independently be integers of 1 to 3
  • a and b may satisfy 0.1 to 10: 1, preferably 0.5 to 5: 1, more preferably 0.8 to 2: 1. It may be to satisfy, but is not particularly limited thereto.
  • the alkynyl functional group may form a triazole ring by a click reaction with the azide functional group of Chemical Formula 3.
  • the p 1 to p 2 are repeating units derived from a monomer having an FG 1 functional group at the terminal, and specifically, the monomer is not particularly limited as long as it is a monomer capable of condensation polymerization or addition polymerization, but is preferably an acrylic type capable of radical polymerization. , It may be one or more monomers selected from methacrylic and vinylic groups.
  • a and b may mean the number of moles of each of p 1 and p 2 repeating units in the first polymer.
  • the ratio of a and b (a:b) may be adjusted by adjusting the molar ratio of the monomers corresponding to the p 1 and p 2 repeating units or by adjusting the polymerization conditions, but is not limited thereto.
  • Chemical Formula 4 according to an embodiment of the present invention may be represented by Chemical Formula 6 below.
  • Ar is a trivalent aromatic radical
  • R 1 to R 2 are independently C 1-50 alkylene, C 3-50 cycloalkylene, C 6-50 arylene, C 3-50 heteroarylene, C 1-50 alkoxycarbonylene or combinations thereof; , wherein the alkylene, cycloalkylene, arylene, heteroarylene and alkoxycarbonylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C 1-20 alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Haloalkyl, C 1-20 Alkoxy, C 1-20 Alkoxycarbonyl, C 3-30 Cycloalkyl, (C 6-30 )Ar(C 1-20 ) It may be substituted with one or more selected from alkyl, C 6-30 aryl, C 3-30 heteroaryl, etc., z and k are integers from 1 to 7, and a and b are integers of 1 or more.
  • R 1 to R 2 may independently be C 1-20 alkylene, C 6-20 arylene, C 1-20 alkoxycarbonylene or a combination thereof, and the alkylene, arylene and heteroarylene is optionally hydroxy, halogen, carboxyl, C 1-7 alkyl, C 1-7 haloalkyl, C 1-7 alkoxy, C 1-7 alkoxycarbonyl, (C 6-20 )ar(C 1-7 )alkyl and C 6-20 It may be substituted with one or more selected from aryl, z and k are integers from 1 to 3, and a and b are 0.1 to 10: 1, preferably 0.5 to 5: 1 may be satisfied.
  • Chemical Formula 6 according to an embodiment of the present invention may be represented by Chemical Formula 7 below.
  • R 2 to R 3 are independently a direct bond or C 1-10 alkylene, and a and b are integers greater than or equal to 1.
  • R 2 to R 3 may independently be C 1-3 alkylene, more preferably R 2 to R 3 may be methylene, and a and b may preferably satisfy a ratio of 0.8 to 2: 1 there is.
  • z and k in Formula 4 refer to the number of FG 1 included in p 1 and p 2 repeating units, respectively. In the case of Formula 7, for example, z may be 2 and k may be 1.
  • FG 1 is an alkynyl functional group
  • FG 3 is an epoxy functional group
  • p 1 to p 2 are repeating units derived from a monomer having an FG 1 functional group at the terminal
  • p 3 has an FG 3 functional group at the terminal.
  • It is a repeating unit derived from a monomer having, z, k and t are independently integers from 1 to 7, and a, b and c are integers greater than or equal to 1.
  • z, k, and t may independently be integers from 1 to 3
  • the ratio of the sum of a and b and c (a+b:c) is 1 to 10: 1, preferably 1 to 7: 1 It may satisfy the ratio of, but is not limited thereto.
  • the epoxy functional group may react chemically with the substrate, and the alkynyl functional group may form a triazole ring through a click reaction with the azide functional group of Chemical Formula 3.
  • p 1 to p 2 may be repeating units derived from a monomer having an FG 1 functional group at the terminal
  • p 3 may be a repeating unit derived from a monomer having an FG 3 functional group at the terminal.
  • the monomers may be condensed. Any monomer capable of polymerization or addition polymerization is not particularly limited, but may be at least one monomer selected from acrylic, methacrylic, and vinyl-based monomers capable of radical polymerization.
  • a to c may mean the number of moles of p 1 to p 3 repeating units in the first polymer.
  • the ratio of a to c may be adjusted by adjusting the molar ratio of the monomers corresponding to the p 1 to p 3 repeating units or by adjusting the polymerization conditions, but is not limited thereto.
  • Chemical Formula 5 according to an embodiment of the present invention may be represented by Chemical Formula 8 below.
  • Ar is a trivalent aromatic radical
  • R 1 , R 2 and R 4 are independently C 1-50 alkylene, C 3-50 cycloalkylene, C 6-50 arylene, C 3-50 heteroarylene, C 1-50 alkoxycarbonylene or these wherein the alkylene, cycloalkylene, arylene, heteroarylene and alkoxycarbonylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 haloalkyl, C 1-20 alkoxy, C 1-20 alkoxycarbonyl, C 3-30 cycloalkyl, (C 6-30 )ar(C 1-20 )alkyl, C 6-30 aryl and C 3-30 heteroaryl, R 5 is hydrogen or C 1-3 alkyl, z, k and t are 1 to 7 is an integer of , and a, b and c are integers greater
  • Ar is a trivalent aromatic radical
  • R 1 , R 2 and R 4 may independently be C 1-20 alkylene, C 6-20 arylene, C 1-20 alkoxycarbonylene or a combination thereof, and the above alkylene, arylene and heteroarylene is optionally hydroxy, halogen, carboxyl, C 1-7 alkyl, C 1-7 haloalkyl, C 1-7 alkoxy, C 1-7 alkoxycarbonyl, (C 6-20 )ar(C 1-7 ) It may be substituted with one or more selected from alkyl and C 6-20 aryl, R 5 is hydrogen or methyl, z and k are integers from 1 to 3, and the sum of a and b and the ratio of c (a+ b:c) may satisfy a ratio of 1 to 10:1, preferably 1 to 7:1.
  • Chemical Formula 8 according to an embodiment of the present invention may be represented by Chemical Formula 9 below.
  • R 2 to R 4 are independently C 1-10 alkylene, R 5 is hydrogen or methyl, and a, b and c are integers greater than or equal to 1.
  • R 2 to R 4 are independently C 1-3 alkylene, R 5 may be methyl, and the ratio of the sum of a and b and c (a+b:c) is 1 to 7:1 It may be that the ratio is satisfied.
  • z, k and t in Formula 5 mean the number of FG 1 and FG 3 included in p 1, p 2 and p 3 repeating units, respectively.
  • z is 2 and k is 1, t may be 1.
  • p 1 to p 3 may independently mean repeating units constituting the first polymer represented by Chemical Formula 2.
  • the p 1 and p 2 repeating units may be independently derived from monomers having one or more FG 1 functional groups at terminals, and in Chemical Formula 5, the p 3 repeating units may have one or more FG 3 terminals. It may be derived from monomers containing functional groups.
  • the FG 1 functional group may be an alkynyl functional group, and the FG 3 functional group may be an epoxy functional group.
  • the type of the monomer is not particularly limited as long as it is capable of copolymerization, and specifically, the type is particularly limited if it is a monomer capable of condensation polymerization or addition polymerization. It doesn't work.
  • it may include monomers such as acrylic, methacrylic, and vinyl-based monomers capable of radical polymerization, but are not limited thereto.
  • the ratio of a and b in Formula 4 may be adjusted by adjusting the molar ratio of the monomers introduced into the polymerization, and the ratio of a to c in Formula 5 may be adjusted. That is, the molar ratio of the monomers introduced into the polymerization and the ratio of the repeating units p 1 to p 3 may be similar or the same. Specifically, the number of moles of repeating unit p 1 corresponds to a, the number of moles of p 2 corresponds to b, and the number of moles of p 3 corresponds to c . When polymerized, a: b: c may be the same as or similar to 2: 2: 1, but is not particularly limited thereto, and the ratio may be adjusted depending on the reactivity of each monomer and polymerization conditions.
  • the type of the second polymer according to an embodiment of the present invention is not particularly limited as long as it has an azide functional group on its side chain.
  • the second polymer may be selected from acrylic, urethane, epoxy, fluorene, carbazole, thiophene, and olefin polymers, but is not limited thereto.
  • the second polymer may be synthesized by polymerizing one or more monomers, and the polymerization may be synthesized in the form of condensation polymerization or addition polymerization, but is not particularly limited, and the monomer has an azide functional group at the terminal and CNT As long as it can wrap the , it can be used without any particular restrictions.
  • the second polymer may prepare a second polymer-CNT composite by lapping CNT, and may preferably be a fluorene-based copolymer.
  • the fluorene-based copolymer may be obtained by copolymerizing two or more fluorene-based monomers.
  • the second polymer is a fluorene-based copolymer, which is a conjugated polymer with electrical conductivity, it is possible to wrap the CNT more effectively, and thus a film formed with high-density CNTs can be produced. CNTs having excellent electrical properties using this Very nice to be able to make transistors.
  • the compound represented by Chemical Formula 3 may be a copolymer including a repeating unit (n) of Chemical Formula 10 and a repeating unit (m) of Chemical Formula 11 below.
  • R 6 to R 7 are independently C 5-50 alkylene, and R 8 to R 9 are independently C 5-50 alkyl.
  • R 6 to R 7 are independently C 5-20 alkylene
  • R 8 to R 9 may be independently C 5-20 alkyl, and in the case of alkylene and alkyl satisfying the number of carbon atoms in the above range, CNTs can be effectively wrapped through ⁇ - ⁇ stacking interaction with the CNT sidewall.
  • the second polymer-CNT composite can be prepared by selectively lapping the sc-SWCNT, and a composite layer is formed using the same.
  • the number average molecular weight of the copolymer including the repeating unit (n) and the repeating unit (m) may be 1,000 to 500,000 Da, preferably 3,000 to 50,000 Da, and more preferably 5,000 to 35,000 Da, but in the present invention It is not limited thereto as long as the desired physical properties are not impaired.
  • the copolymer including the repeating unit (n) and the repeating unit (m) may be a random copolymer in which each repeating unit is randomly polymerized, or an alternating copolymer in which each repeating unit is crossed and bonded. And, preferably, it may be a random copolymer.
  • n+m may be 1, and n is 0.9 or less, 0.7 or less, preferably 0.5 or less. .
  • the copolymer including the repeating unit (n) and the repeating unit (m) may have more improved selectivity to sc-SWCNTs, and through this, CNTs having sc-SWCNTs having a higher density. film can be coated.
  • the transistor coated with the high-density sc-SWCNTs it is good that more improved electrical characteristics can be exhibited.
  • the mole fraction may be used without significant limitation if it is a commonly used or known method for analyzing the mole fraction of a copolymer, and can be specifically confirmed through NMR analysis.
  • the copolymer including the repeating unit (n) of Formula 10 and the repeating unit (m) of Formula 11 may be represented by Formula 14 below.
  • R 6 and R 7 are independently C 5-20 alkylene
  • R 8 , R 9 , R 18 and R 19 may be independently C 5-20 alkyl
  • the n may be 0.5 or less, 0.4 or less, more preferably 0.3 or less, 0.2 or less, or 0.1 or less
  • the upper limit is not particularly limited, but may be 0.0001 or more, but if the physical properties intended by the present invention are not impaired, this Not limited.
  • the copolymer may be a random copolymer in which each repeating unit is randomly polymerized, or an alternating copolymer in which each repeating unit is crossed and bonded, preferably a random copolymer.
  • the CNT transistor according to an embodiment of the present invention may further include a self-assembled monolayer (SAM) between the substrate and the polymer layer formed from the first polymer.
  • SAM self-assembled monolayer
  • the self-assembled monolayer includes a material that easily reacts with the surface of the substrate layer, for example, a silane coupling agent, and a photopolymerization initiator that can effectively absorb energy to form radicals to cause a crosslinking reaction, for example, a benzophenone structure. It may be a unit derived from a compound.
  • the self-assembled monolayer (SAM) of the CNT transistor according to an embodiment of the present invention may be a self-assembled monolayer formed from a compound represented by Formula 12 below.
  • R 10 is C 1-10 alkylene, and R 11 to R 13 are independently hydroxy, halogen, C 1-10 alkyl, C 1-10 haloalkyl, C 1-10 alkoxy or C 1 -10 alkoxycarbonyl.
  • R 10 is C 1-7 alkylene, R 11 to R 13 may independently be halogen, C 1-7 alkyl, or C 1-7 haloalkyl, and the halogen may be Cl or F; More preferably, Formula 12 may be represented by Formula 13 below.
  • the compounds represented by Chemical Formulas 12 and 13 include a benzophenone structure and can effectively absorb an energy beam to react with an alkyl chain of a polymer in contact with electrons of an n-orbital of a carbonyl group of benzophenone. Accordingly, the compounds represented by Chemical Formulas 12 and 13 and the first polymer may be crosslinked by energy beam irradiation, and the energy beam may be ultraviolet (UV) as a non-limiting example.
  • UV ultraviolet
  • the self-assembled monolayer may be formed from the compound represented by Formula 12, and the self-assembled monolayer is chemically bonded to the substrate and cross-linked with the first polymer, thereby forming a polymer formed from the first polymer on the substrate.
  • the metal electrode of the CNT transistor according to an embodiment of the present invention is 1 selected from the group consisting of Pt, Al, Au, Cu, Cr, Ni, Ru, Mo, V, Zr, Ti, W, and alloys thereof.
  • Species or ITO Indium tin oxide), AZO (Al-doped ZnO), IZO (Indium zinc oxide), FTO (F-doped SnO 2 ), GZO (Ga-doped ZnO), ZTO (zinc tin oxide), GIO ( gallium indium oxide), ZnO, Pd, Ag, and combinations thereof.
  • the metal electrode may include a source electrode and a drain electrode, and a transistor may be manufactured by forming a metal electrode on the composite layer.
  • the thickness of the metal electrode may be 20 to 100 nm, preferably 20 to 80 nm, but is not limited thereto.
  • the present invention is a polymer layer formed from a first polymer on a substrate; a composite layer formed from a second polymer-CNT composite on the polymer layer; and a metal electrode formed on the composite layer, wherein the second polymer-CNT composite is a CNT lapped by the second polymer, and the polymer layer and the composite layer are connected through triazole.
  • a manufacturing method of is a manufacturing method of.
  • a method of manufacturing a CNT transistor includes the steps of (a) coating and immobilizing a first polymer on a substrate; (b) immersing the substrate coated with the first polymer in a solution of the second polymer-CNT composite; (c) forming a polymer layer and a composite layer by a click reaction between the first polymer and the second polymer; and (d) forming a source electrode and a drain electrode on the composite layer.
  • the first polymer may be represented by Chemical Formula 2
  • the second polymer may be represented by Chemical Formula 3
  • the first polymer and the second polymer may be represented by Chemical Formula 3.
  • a detailed description of the polymer is the same as described above.
  • the step (a) includes: (a-1) washing the substrate with a solvent; (a-2) coating a self-assembled monolayer (SAM); (a-3) coating the first polymer; (a-4) UV curing step; and (a-5) washing the unfixed compound on the substrate with a solvent.
  • SAM self-assembled monolayer
  • washing the substrate with a solvent may be performed to remove impurities on the surface of the substrate, and the solvent may be a commonly used inorganic solvent or organic solvent. Solvents or mixtures thereof may be used.
  • the solvent may be one or more selected from the group consisting of water, nitric acid, sulfuric acid, hydrogen peroxide, acetone, IPA, THF, benzene, chloroform and toluene, or a mixture thereof, preferably a mixture of sulfuric acid and hydrogen peroxide It may be washed first with water, washed secondly with water, and washed thirdly with toluene, and the weight ratio of sulfuric acid to hydrogen peroxide may satisfy 1 to 9:9 to 1, but is not limited thereto.
  • the step of (a-2) coating the self-assembled monolayer may be performed by spin coating, immersion coating, gas phase deposition, doctor blade coating, or curtain coating.
  • it may be a dip coating method, and the dip coating method may include a process of immersing the washed substrate in a self-assembled monolayer solution for 1 to 20 hours, preferably for 3 to 10 hours. .
  • the immersion process may be to wash with one or more solvents selected from the group consisting of acetone, methanol, ethanol, isopropyl alcohol (IPA), toluene and tetrahydrofuran (THF), etc., preferably ethanol It may be the first washing with and the second washing with toluene. Whether or not the self-assembled monolayer is coated can be confirmed by measuring the contact angle, and when the contact angle is 40° or more, it can be determined that the self-assembled monolayer is coated.
  • solvents selected from the group consisting of acetone, methanol, ethanol, isopropyl alcohol (IPA), toluene and tetrahydrofuran (THF), etc.
  • the self-assembled monolayer solution may include a compound represented by Chemical Formula 12 and a solvent, and the concentration of the compound represented by Chemical Formula 12 in the self-assembled monolayer solution M may preferably be 0.001 to 3 M, but is not particularly limited.
  • Formula 12 may be represented by Formula 13, and descriptions of Formulas 12 and 13 are the same as described above.
  • the solvent of the self-assembled monolayer solution may be a solvent that does not react with the compound represented by Formula 12, and non-limiting examples include aromatic hydrocarbons including toluene, xylene, and mesitylene; cycloalkanes including cyclohexane, cycloheptane, cyclooctane and cyclononane; It may be one or more selected from alkanes including hexane, heptane, octane, nonane, and decane, and alkyl alcohols including methanol, ethanol, 1-propanol, and 2-propanol, and the like, and may preferably be toluene. It is not particularly limited as long as the solvent does not react with the compound represented by .
  • (a-3) coating the first polymer may include spin coating, dip coating, dropping, spray coating, solution casting, or bar coating of the first polymer. , It may be coating by one method selected from roll coating and gravure coating, and may be preferably selected from spin coating, spray coating, solution casting, and roll coating. In addition, coating may be performed by preparing a coating solution containing the first polymer.
  • the coating solution may include the first polymer and a solvent, and the solvent is not particularly limited as long as the first polymer is dissolved, but non-limiting examples include ethyl acetate (EA, ethyl acetate), toluene, acetone, 1
  • EA ethyl acetate
  • DMA dimethylacetamide
  • DMF dimethylformamide
  • THF Tetrahydrofuran
  • chloroform tetrahydrofuran
  • It can be one or more, and preferably it can be 1,4-dioxane or chloroform.
  • the coating solution may include the first polymer at a concentration of 0.1 to 40 mg/ml, but is not limited thereto, and the concentration may be adjusted according to a desired coating thickness.
  • An appropriate method may be selected from among the above methods by preparing a coating solution containing the first polymer, depending on the characteristics of the coating solution and the purpose of use.
  • the first polymer may be represented by Chemical Formula 2, and specifically, Chemical Formula 2 may be represented by Chemical Formula 4. there is.
  • Chemical Formula 4 may be represented by Chemical Formula 6, and Chemical Formula 6 may be represented by Chemical Formula 7. Descriptions of Chemical Formulas 2, 4, 6 and 7 are the same as described above.
  • the UV curing step (a-4) involves fixing a polymer layer formed from the first polymer on a substrate by crosslinking the compound represented by Chemical Formula 12 and the first polymer.
  • the UV curing time may be made for 0.1 to 30 minutes, but is not limited thereto.
  • the UV curing may be performed using a 365 nm UV lamp, and the UV lamp may have an intensity of 500 to 1500 mJ/cm 2 , but is not limited thereto.
  • the UV curing step may include a process of forming a pattern on the substrate layer through a washing process after forming a UV curing mask pattern using a patterned mask.
  • a CNT pattern can be formed on a substrate, which enables various circuit designs and can be applied not only to transistors but also to various industrial fields such as semiconductor devices and displays.
  • the substrate layer may be washed with a solvent to remove unreacted compounds.
  • the solvent may be a commonly used solvent, and is not particularly limited as long as the solvent dissolves the unreacted compound, but non-limiting examples include toluene, acetone, 1,4-dioxane, EA, DMA, DMF, THF And one or more solvents selected from chloroform and the like may be used.
  • the step (a) includes (a'-1) washing the substrate with a solvent; (a'-2) coating the first polymer; (a'-3) heat treatment step; and (a'-4) washing the unfixed compound on the substrate with a solvent.
  • the step of washing the substrate with a solvent (a'-1) is performed to remove organic and inorganic contaminants remaining on the substrate, and the solvent is commonly used.
  • An inorganic solvent, an organic solvent, or a mixture thereof may be used. Examples of the specific compound may be the same as or different from the solvent used in (a-1) washing the substrate with the solvent.
  • the step of (a′-2) coating the first polymer may be performed in the same manner as the step of (a-3) coating the first polymer.
  • the first polymer may be represented by Chemical Formula 2, and specifically, Chemical Formula 2 may be represented by Chemical Formula 5.
  • Chemical Formula 5 may be represented by Chemical Formula 8
  • Chemical Formula 8 may be represented by Chemical Formula 9. Descriptions of Chemical Formulas 2, 5, 8 and 9 are the same as described above.
  • the substrate and the first polymer are chemically bonded to form a polymer layer formed from the first polymer on the substrate.
  • the heat treatment temperature is 100 to 150 ° C
  • the heat treatment time may be 1 hour or more, but the temperature and time may be adjusted according to the thickness of the polymer layer, etc. and the range of time is not particularly limited.
  • the substrate layer may be washed with a solvent to remove unreacted compounds.
  • the solvent may be a commonly used solvent, and is not particularly limited as long as the solvent dissolves the unreacted compound, but non-limiting examples include toluene, acetone, 1,4-dioxane, EA, DMA, DMF, THF And one or more solvents selected from chloroform and the like may be used.
  • the second polymer-CNT composite solution according to an embodiment of the present invention may include the second polymer, CNT, and a solvent.
  • the second polymer-CNT composite solution may be a solution in which the second polymer wrapped with CNT is dissolved in a solvent.
  • the CNTs include single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes, multi-walled carbon nanotubes, and bundled carbon nanotubes (Rope).
  • Carbon Nanotube may be one or more selected from the group consisting of, or may be a single-walled carbon nanotube (SWCNT).
  • SWCNT single-walled carbon nanotube
  • it may be a conductive single-walled carbon nanotube (m-SWCNT), a semiconducting single-walled carbon nanotube (sc-SWCNT), or a mixture thereof, and when using a semiconducting single-walled carbon nanotube (sc-SWCNT) , which can be desirable as it can fabricate CNT transistors with better electrical performance.
  • a CNT film may be formed on a base substrate by selecting CNTs having suitable physical properties according to the application field.
  • the CNT may have an outer diameter of 0.1 nm or more, preferably 0.1 to 10 nm, and more preferably 0.1 to 5 nm, but is not particularly limited as long as the dispersibility is not affected when preparing the second polymer-CNT composite solution.
  • the solvent of the second polymer-CNT composite solution is not particularly limited as long as the second polymer of the present invention can be dissolved, and preferably a non-polar solvent can be used.
  • Non-limiting examples of the non-polar solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene and aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane and methylcyclohexane (MCH), preferably Toluene or methylcyclohexane may be used.
  • Polar solvents such as chloroform or tetrahydrofuran (THF) may also be used, but are not limited thereto.
  • the method for preparing the second polymer-CNT composite solution according to an embodiment of the present invention may include dissolving the second polymer in a solvent and then dispersing the CNTs.
  • the second polymer may be included at a concentration of 0.1 to 30 mg/ml, more preferably 0.1 to 20 mg/ml, relative to the solvent, but is not limited thereto, and the CNT may be at a concentration of 0.05 to 5 mg/ml.
  • the second polymer is preferably completely dissolved in a solvent, and may be dissolved in a temperature range of 50 to 100 °C.
  • the second polymer (second polymer-CNT composite) wrapped in the CNT is separated through centrifugation, and may be manufactured through a filtration process and a redispersion process, but is not limited thereto.
  • the concentration of the second polymer-CNT composite in the second polymer-CNT composite solution after the redispersion process may be 0.001 to 10 mg/ml, and adjusting the concentration to control the density of the CNT film It may be, but is not limited thereto.
  • the solvent used in the redispersion process may be the same as or different from the example of the specific compound of the solvent of the second polymer-CNT composite solution described above, and the dispersion and redispersion process may be carried out through ultrasonic treatment, but It is not limited.
  • the substrate is manufactured with the second polymer-CNT composite solution satisfying the above range, a CNT film of appropriate density can be formed on the substrate layer, and a highly stable and high-density CNT film for the purpose of the present invention can be manufactured.
  • the prepared second polymer-CNT composite solution may be used in step (b) immersing the coated substrate in the second polymer-CNT composite solution.
  • the second polymer may be a copolymer containing the repeating unit (n) of Formula 10 and the repeating unit (m) of Formula 11 at the same time, and the description of the copolymer is described above. Same as described.
  • the step of (c) forming a polymer layer and a composite layer by a click reaction between the first polymer and the second polymer is performed through a heating or ultrasonic treatment process under a copper catalyst.
  • a polymer layer formed from the first polymer and a composite layer formed from the second polymer-CNT composite may be formed, and the polymer layer and the composite layer may be connected through a triazole ring.
  • it may be ultrasonic treatment at an intensity of 90 to 120 W at a temperature of 50 to 60 ° C.
  • the ultrasonic treatment time is 1 minute or more, preferably 2 minutes to 6 hours, more preferably 5 minutes to 2 minutes
  • the temperature, intensity, and time are not particularly limited as long as the desired physical properties in the present invention are not impaired.
  • the reaction may be performed by adjusting the time in various ways to realize a desired CNT film density.
  • the density of the CNT film can be confirmed by Raman spectroscopy or by observing the surface of the coating layer through a scanning electron microscope (SEM) or an optical microscope.
  • the process of the click reaction between the first polymer and the second polymer may be represented by Reaction Scheme 1, and may be specifically represented by Reaction Scheme 2 above. Descriptions of Reaction Schemes 1 and 2 are the same as described above.
  • the click reaction when manufacturing a CNT transistor through the click reaction, it is possible to uniformly coat a high-density CNT film in a short time, which not only makes the work easy and efficient, but also makes the CNT film chemically bond. It is good that the CNT film is not peeled off even after washing because the adhesion is excellent and the stability to water and organic solvent is secured by being coated on the substrate layer through the process.
  • the click reaction when used, the CNT film is uniformly coated so that reproducibility between devices is improved. It is even better that an excellent and highly reliable CNT transistor can be manufactured.
  • a step of washing the unreacted compound with an organic solvent may be performed, which is a catalyst, monomer and polymer used in the reaction. It may be performed to prepare a high-purity CNT film by removing unreacted compounds such as
  • the organic solvent may be used without particular limitation as long as it is a commonly used solvent, and one or more solvents selected from toluene, acetone, 1,4-dioxane, EA, DMA, DMF, THF, and chloroform may be used as non-limiting examples. there is.
  • the cleaning process may be performed through ultrasonic cleaning, and the ultrasonic intensity may be strongly performed at 170 to 230W.
  • the high-density CNT transistor according to the present invention maintains a high-density CNT film even after an ultrasonic cleaning process, thereby securing stability against water and organic solvents, which is very good.
  • (d) forming a source electrode and a drain electrode on the composite layer may be performed using a known or conventional electrode forming method. For example, a method of heat-treating the composite layer formed from the second polymer-CNT composite at 100 to 200 ° C. for 10 to 60 minutes, and then depositing a source electrode and a drain electrode using a shadow mask.
  • the source electrode and the drain electrode may include at least one selected from the group consisting of Pt, Al, Au, Cu, Cr, Ni, Ru, Mo, V, Zr, Ti, W, and alloys thereof, or ITO (Indium tin oxide), AZO (Al-doped ZnO), IZO (Indium zinc oxide), FTO (F-doped SnO 2 ), GZO (Ga-doped ZnO), ZTO (zinc tin oxide), GIO (gallium indium oxide), It may be an electrode formed by at least one selected from the group consisting of ZnO, Pd, Ag, and combinations thereof, and the thickness of the source electrode and the drain electrode may be 20 to 100 nm, preferably 20 to 80 nm, but is limited thereto It is not, and the type and thickness of the electrode can be adjusted according to the use.
  • the CNT transistor manufactured through the above manufacturing method may be a field effect transistor (FET), and the electrical characteristic curves (output curve and transfer curve) measured between transistor elements manufactured on the same substrate layer are uniformly displayed. It is good to ensure reproducibility and reliability.
  • FET field effect transistor
  • the blinking current ratio of the transfer curve according to the present invention may be 10 3 or more, preferably 10 4 to 10 9 , and when the above range is satisfied, the amplifying effect of the transistor of the present invention can be more effectively exhibited.
  • An acrylate copolymer represented by Formula 6 below according to an embodiment of the present invention may be provided.
  • Chemical Formula 6 is the same as described above, and Chemical Formula 6 may be represented by the following compound, but is not limited thereto.
  • a and b of the compound are the same as those described in Chemical Formula 6 above.
  • An acrylate copolymer represented by Formula 8 below according to an embodiment of the present invention may be provided.
  • Chemical Formula 8 is the same as described above, and Chemical Formula 8 may be represented by the following compound, but is not limited thereto.
  • A, b and c of the compound are the same as described in Chemical Formula 8 above.
  • Ar may be two identical R 1 connected to each other, or two different R 1 may be connected to each other.
  • the R 1 may include z FG 1 , and when two different R 1 are connected to Ar, z of the different R 1 may independently be an integer of 1 to 7.
  • the obtained polymer was analyzed by 1 H NMR to confirm that the target product acrylate copolymer (i) was prepared, and analyzed by GPC to confirm that the number average molecular weight (Mn) was 16,762 Da and the PDI was 3.3.
  • the obtained polymer was analyzed by 1 H NMR to confirm that the target product acrylate copolymer (ii) was prepared, and analyzed by GPC to confirm that the number average molecular weight (Mn) was 17,800 Da and the PDI was 2.11.
  • Copolymer (iii) in the form of a yellow solid was obtained by precipitation and filtration using chloroform and methanol. (Yield 45%)
  • the number average molecular weight of the copolymer was measured to be 28000 Da.
  • Copolymer (IV) in the form of a yellow solid was obtained by precipitation and filtration using chloroform and methanol. (Yield 53%)
  • the number average molecular weight of the copolymer (IV) was measured to be 31000 Da. Through NMR analysis, it was confirmed that the n was about 0.3.
  • Copolymer (V) in the form of a yellow solid was obtained by precipitation and filtration using chloroform and methanol. (Yield 61%)
  • the number average molecular weight of the copolymer (V) was measured to be 37000 Da. Through NMR analysis, it was confirmed that the n was about 0.1.
  • the fluorene-based copolymer (iii) of Preparation Example 4 was added at a concentration of 1 mg/ml to 20 ml of methylcyclohexane (MCH) and heated at 80° C. for 1 hour to completely dissolve. After cooling, 20 mg of Purified Powder SWCNT (Nanointegris Inc., RN-220) was added and dispersed with an ultrasonic processor (Sonics & Materials Inc., VCX-750, 750W) at room temperature, and centrifugal separator (Hanil Scientific Inc. , Supra R30) and centrifuged at 85,000 g for 1 hour.
  • MCH methylcyclohexane
  • the solution excluding the precipitate was filtered through a 0.20 ⁇ m MCE (Mixed Cellulose Ester) membrane to obtain a fluorene-based copolymer (iii) wrapping sc-SWCNTs. After washing the obtained pellet several times, it was added to 10 ml of toluene at a concentration of 0.02 mg/ml, sonicated for 5 minutes and redispersed to prepare a second polymer-CNT composite solution.
  • MCE Mated Cellulose Ester
  • a suspension was prepared by putting 2 g of the ABP and 20 mL of dimethyl chlorosilane in a flask and stirring. 10 mg of Pt—C (10% Pt) was added thereto, and the mixture was stirred and refluxed at 50° C. for 8 hours. After dissolving the reactants in toluene at a concentration of 0.01 M, filtering to remove the catalyst, a BPS solution, which is a self-assembled monolayer solution in the form of an oil containing the compound BPS, was obtained.
  • a solution in which the acrylate copolymer (i) of Preparation Example 2 was dissolved in 1,4-dioxane at a concentration of 5 mg/ml was spin-coated at 1000 rpm for 50 seconds, and 727 mJ/ml
  • a substrate fixing step was performed by UV curing for 1 minute at an intensity of cm 2 .
  • ultrasonic cleaning was performed in chloroform for 1 hour to remove unfixed compounds on the substrate layer, and after removing the solvent with nitrogen gas, heat treatment was performed at 100° C. for 10 minutes.
  • a CNT transistor according to Example 1 was manufactured by depositing Au to a thickness of 60 ⁇ m using a shadow mask on a completely dried substrate to form a source electrode and a drain electrode.
  • the shadow mask used and the manufactured CNT transistor are shown in FIG. 2 .
  • Example 1 the same procedure as in Example 1 was performed except that the click reaction was performed by ultrasonic treatment at an intensity of 110 W for 7 minutes.
  • Example 3 the same procedure as in Example 3 was performed except that the click reaction was performed by ultrasonic treatment at an intensity of 110 W for 7 minutes.
  • a 100 nm SiO 2 substrate layer (Chung King Enterprises) was cleaned with a solution of a mixture of sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ) in a ratio of 7:3, and then washed again with water and toluene. .
  • the second polymer-CNT composite solution of Preparation Example 7 was spin-coated on the substrate layer at 2000 rpm and dried on a hot plate. After the film was coated by repeating the above process three times, ultrasonic cleaning was performed in toluene to remove the substrate and unreacted compounds, and after removing the solvent with nitrogen gas, heat treatment was performed at 150° C. for 30 minutes.
  • a CNT transistor according to Comparative Example 1 was manufactured by depositing Au to a thickness of 60 ⁇ m using a shadow mask on a completely dried substrate to form a source electrode and a drain electrode. Electrical characteristic curves (output curve and transfer curve) of all elements of the CNT transistor according to Comparative Example 1 are shown in FIG. 6 .
  • Example 1 on the substrate layer coated with the acrylate copolymer (i), the second polymer-CNT composite solution of Preparation Example 7 was spin-coated at 2000 rpm, not a click reaction, and dried on a hot plate. After the film was coated by repeating the above process twice, ultrasonic cleaning was performed in toluene to remove the substrate and unreacted compounds, and after removing the solvent with nitrogen gas, heat treatment was performed at 150° C. for 30 minutes.
  • a CNT transistor according to Comparative Example 2 was manufactured by depositing Au to a thickness of 60 ⁇ m using a shadow mask on a completely dried substrate to form a source electrode and a drain electrode. Electrical characteristic curves (output curve and transfer curve) of all elements of the CNT transistor according to Comparative Example 2 are shown in FIG. 7 .
  • Example 3 the second polymer-CNT composite solution of Preparation Example 7 was spin-coated on the substrate layer coated with the acrylate copolymer (ii) at 2000 rpm, not a click reaction, and dried on a hot plate. After the film was coated by repeating the above process twice, ultrasonic cleaning was performed in toluene to remove the substrate and unreacted compounds, and after removing the solvent with nitrogen gas, heat treatment was performed at 150° C. for 30 minutes.
  • a CNT transistor according to Comparative Example 3 was manufactured by depositing Au to a thickness of 60 ⁇ m using a shadow mask on a completely dried substrate to form a source electrode and a drain electrode.
  • Comparative Example 3 the same procedure as in Comparative Example 3 was performed except that the spin coating process was repeated 7 times instead of 2 times.
  • the hole mobility of the transistor according to Comparative Example 1 was measured as low as a maximum of 0.06 cm 2 /Vs and an average of 0.02 cm 2 /Vs, whereas the hole mobility of the transistor according to Example 1 was a maximum of 4.20 cm 2 /Vs, An average of 2.92 cm 2 / Vs and an on / off ratio of 1.76 x 10 4 , the maximum hole mobility of the transistor according to Example 3 was 5.07 cm 2 / Vs, an average of 3.23 cm 2 / Vs and an on / off ratio of 1.76 x 10 4 In that, the excellent electrical performance of the transistor according to the present invention could be confirmed. In addition, when the electrical characteristic curve of Example 2 was measured under a nitrogen atmosphere rather than in the air, the maximum hole mobility was measured as 10.11 cm 2 /Vs, confirming a more excellent electrical effect.
  • the CNT transistor according to the present invention can uniformly coat the CNT film at high density on the substrate layer, and through this, it is stable in organic solvents, and at the same time, reproducibility and reliability between devices can be remarkably improved.
  • electrical characteristic curves between elements can be uniformly measured, and through this, reliability of the transistor can be secured.
  • Transistors in order to solve the problems of conventional CNT-based transistors that are easily peeled off, vulnerable to organic solvents, and have insufficient reliability between devices, a CNT transistor was manufactured using a click reaction, and the reproducibility between the devices is excellent and the reliability is high.
  • Transistors can be used in various fields such as electronic devices such as displays and diagnostic devices such as biosensors and gas sensors.

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  • Thin Film Transistor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Un transistor NTC selon la présente invention peut présenter une stabilité élevée vis-à-vis de l'eau ou de solvants organiques, un film NTC étant formé uniformément à une densité élevée à l'aide d'une réaction click. En particulier, des transistors NTC classiques fabriqués par revêtement par pulvérisation et par enduction centrifuge d'une solution NTC présentent d'importantes différences de propriétés physiques entre des dispositifs de telle sorte que la reproductibilité et la fiabilité ne peuvent pas être assurées, tandis que dans le cas du transistor NTC selon la présente invention, un transistor NTC peut être fabriqué avec une reproductibilité et une fiabilité élevées par un procédé relativement simple.
PCT/KR2022/012825 2021-09-06 2022-08-26 Transistor ntc utilisant une réaction click et son procédé de fabrication Ceased WO2023033465A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130035571A (ko) * 2011-09-30 2013-04-09 한국화학연구원 높은 점멸비를 가지는 탄소나노튜브 네트워크 트랜지스터 소자 및 그 제조방법
KR20130054982A (ko) * 2010-07-28 2013-05-27 가부시끼가이샤 도시바 패턴 형성 방법 및 중합체 알로이 기재
KR20140033555A (ko) * 2012-08-29 2014-03-19 삼성전자주식회사 탄소나노튜브 분리 방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180048236A (ko) * 2016-11-02 2018-05-10 주식회사 나노웨어러블 랩핑된 탄소나노튜브가 포함된 유기반도체층, 이의 제조방법 및 이를 이용한 박막트랜지스터

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130054982A (ko) * 2010-07-28 2013-05-27 가부시끼가이샤 도시바 패턴 형성 방법 및 중합체 알로이 기재
KR20130035571A (ko) * 2011-09-30 2013-04-09 한국화학연구원 높은 점멸비를 가지는 탄소나노튜브 네트워크 트랜지스터 소자 및 그 제조방법
KR20140033555A (ko) * 2012-08-29 2014-03-19 삼성전자주식회사 탄소나노튜브 분리 방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUAMING LI, FUYONG CHENG, ANDY M. DUFT, ALEX ADRONOV: "Functionalization of Single-Walled Carbon Nanotubes with Well-Defined Polystyrene by "Click" Coupling", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 127, no. 41, 1 October 2005 (2005-10-01), pages 14518 - 14524, XP055092760, ISSN: 00027863, DOI: 10.1021/ja054958b *
JIN HAN, CHAO GAO: "Functionalization of carbon nanotubes and other nanocarbons by azide chemistry", NANO-MICRO LETTERS, vol. 2, no. 3, 1 January 2010 (2010-01-01), pages 213 - 226, XP055730087, DOI: 10.5101/nml.v2i3.p213-226 *

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