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WO2023191534A1 - Film de cnt utilisant une réaction click, capteur de gaz hydrogène à base de cnt l'utilisant, et son procédé de fabrication - Google Patents

Film de cnt utilisant une réaction click, capteur de gaz hydrogène à base de cnt l'utilisant, et son procédé de fabrication Download PDF

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WO2023191534A1
WO2023191534A1 PCT/KR2023/004256 KR2023004256W WO2023191534A1 WO 2023191534 A1 WO2023191534 A1 WO 2023191534A1 KR 2023004256 W KR2023004256 W KR 2023004256W WO 2023191534 A1 WO2023191534 A1 WO 2023191534A1
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polymer
formula
hydrogen gas
gas sensor
layer
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PCT/KR2023/004256
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Korean (ko)
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임보규
박종목
정서현
정유진
김예진
전승주
김가영
이혜민
기르마헤녹
박광훈
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00

Definitions

  • the present invention relates to a CNT film using a click reaction and a CNT-based hydrogen gas sensor using the same. Specifically, it has excellent stability against water or organic solvents, has high reliability manufactured through a click reaction, and is capable of sensing even low concentrations of hydrogen gas with high sensitivity. This relates to a possible CNT-based hydrogen gas sensor and its manufacturing method.
  • Hydrogen energy which is emerging due to the depletion of fossil fuels and environmental pollution problems, has the potential to be used in almost all fields used in the current energy system, including basic industrial materials, general fuel, hydrogen cars, hydrogen airplanes, fuel cells, and nuclear fusion energy. I have it.
  • hydrogen gas has a wide explosive concentration range (4-75%) and small ignition energy, so it is easily ignited by even the slightest static electricity, so even a small amount of hydrogen gas leaked can be very dangerous. Accordingly, in order to reduce major accidents and casualties caused by hydrogen leaks, high-performance gas sensors that can quickly and accurately detect hydrogen gas are required.
  • the adhesion to the substrate is good and the CNT film is formed at high density and uniformity, resulting in excellent inter-device reliability and excellent stability against water or organic solvents, while at the same time excellent selectivity, sensitivity and fast response to hydrogen gas at room temperature.
  • the present invention aims to provide a CNT-based hydrogen gas sensor that has excellent stability and high reliability in organic solvents and exhibits excellent selectivity, sensitivity and fast response speed to hydrogen gas. .
  • Another object of the present invention is to provide a method of manufacturing a CNT-based hydrogen gas sensor using a click reaction, which is relatively easy to process.
  • the present inventors developed a hydrogen gas sensor in which a high-density CNT film has excellent stability against water or organic solvents and at the same time can realize excellent selectivity, sensitivity, and fast response speed to hydrogen gas at room temperature.
  • a hydrogen gas sensor is manufactured using a click reaction
  • the CNT film is formed at high density and uniformity, and has excellent stability against water or organic solvents, so it does not peel off even after washing and is reliable.
  • the present invention was completed by discovering that it is possible to manufacture a hydrogen gas sensor that is not only excellent, but also exhibits excellent selectivity, sensitivity, and fast response speed to hydrogen gas.
  • the present invention relates to a substrate; and a hydrogen gas sensor including a sensing unit, wherein the sensing unit includes a polymer layer formed from a first polymer on the substrate; A composite layer formed from a second polymer-CNT composite on the polymer layer; a metal electrode formed on the composite layer; A palladium nanoparticle layer formed on the composite layer; and a polymer coating layer located on the palladium nanoparticle layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer, and the polymer layer and the composite layer are connected through triazole.
  • the sensing unit includes a polymer layer formed from a first polymer on the substrate; A composite layer formed from a second polymer-CNT composite on the polymer layer; a metal electrode formed on the composite layer; A palladium nanoparticle layer formed on the composite layer; and a polymer coating layer located on the palladium nanoparticle layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer, and
  • the metal electrode includes a source electrode and a drain electrode spaced apart from each other on the composite layer, and the palladium nanoparticle layer may be located in an area where the source electrode and the drain electrode are spaced apart.
  • the polymer coating layer may include an acrylate-based polymer.
  • the polymer coating layer may include non-porous polymethyl methacrylate.
  • the triazole may be represented by the following formula (1).
  • connection points with different layers is each independently a connection point with the first polymer of the polymer layer or the second polymer of the composite layer, and the two * are connection points with different layers.
  • the first polymer is represented by the following formula (2)
  • the second polymer is represented by the following formula (3)
  • the triazole is produced by a click reaction between the first polymer and the second polymer. is formed, and the click reaction can be expressed as Scheme 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.
  • Formula 2 may be expressed as Formula 4 or 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 a monomer having a FG 1 functional group at the end;
  • p 3 is a repeating unit derived from a monomer having a 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.
  • Formula 4 may be represented by Formula 6 below, and Formula 5 may be represented by Formula 8 below.
  • Ar is a trivalent aromatic radical
  • R 1 , R 2 and R 4 are independently of each other C 1-50 alkylene, C 3-50 cycloalkylene, C 6-50 arylene, C 3-50 heteroarylene, C 1-50 alkoxycarbonylene or It is a combination of these;
  • alkylene, cycloalkylene, arylene, heteroarylene and alkoxycarbonylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C 1-20 alkyl, C 2-20 alkyl.
  • FG 1 is an alkynyl functional group
  • FG 3 is an epoxy functional group
  • z, k and t are independently integers from 1 to 7;
  • a, b and c are independently integers of 1 or more.
  • Formula 6 may be represented by Formula 7 below, and Formula 8 may be represented by Formula 9 below.
  • R 2 to R 4 are each independently C 1-10 alkylene
  • R 5 is hydrogen or methyl
  • a, b and c are independently integers of 1 or more.
  • the second polymer may be a fluorene-based copolymer.
  • Formula 3 may be a copolymer containing a repeating unit (n) of Formula 10 below and a repeating unit (m) of 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 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 relates to a substrate; and a hydrogen gas sensor including a sensing unit, wherein the sensing unit includes a polymer layer formed from a first polymer on the substrate; A composite layer formed from a second polymer-CNT composite on the polymer layer; a metal electrode formed on the composite layer; A palladium nanoparticle layer formed on the composite layer; and a polymer coating layer located on the palladium nanoparticle layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer, and the polymer layer and the composite layer are connected through triazole.
  • a method of manufacturing a hydrogen gas sensor can be provided.
  • the manufacturing method of the hydrogen gas sensor is
  • step (e) may include thermal evaporation under temperature conditions lower than the melting point of palladium nanoparticles.
  • the temperature condition may be 80 to 500°C.
  • step (f) may include dissolving the polymer in a solvent and then coating and drying the palladium nanoparticle layer.
  • the solvent may be a halogenated alkoxy benzene compound.
  • 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 compound unfixed to the substrate with a solvent.
  • SAM self-assembled monolayer
  • the first polymer in step (a-3), may be represented by the following formula (4).
  • FG 1 is an alkynyl functional group
  • p 1 to p 2 are repeating units derived from a monomer having a FG 1 functional group at the end;
  • z and k are integers from 1 to 7;
  • a and b are integers greater than or equal to 1.
  • step (a-4) may further include a pattern forming step.
  • 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 first polymer in step (a'-2), may be represented by the following formula (5).
  • 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 a FG 1 functional group at the end;
  • p 3 is a repeating unit derived from a monomer having a 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 hydrogen gas sensor according to the present invention uses a click reaction to form a CNT film at high density and uniformity, so it can have high stability against water or organic solvents.
  • a click reaction to form a CNT film at high density and uniformity, so it can have high stability against water or organic solvents.
  • the hydrogen gas sensor according to the present invention provides hydrogen gas with high reproducibility and reliability in a relatively simple method.
  • the present invention uses a click reaction to form a CNT film at high density and uniformity, and has excellent stability in water or organic solvents, so it does not peel off even after washing, and is not only highly reliable, but also has excellent selectivity, sensitivity and stability to hydrogen gas.
  • a hydrogen gas sensor with a fast response speed can be manufactured.
  • FIG. 1 is a schematic diagram briefly showing a hydrogen gas sensor according to an embodiment of the present invention.
  • Figure 2 is an image measuring the contact angle of the coating layer after coating the self-assembled monolayer (SAM) in Example 1 of the present invention.
  • Figure 3 shows the results of ultraviolet-visible spectroscopy (UV-Vis spectroscopy) before and after UV curing the acrylate copolymer (i) solution coated in Example 1 according to the present invention and washing with a solvent. is a graph showing, and (b) is a graph showing the results of ultraviolet-visible spectroscopy analysis before and after heat curing the acrylate copolymer (ii) solution coated in Example 2 according to the present invention and then washing with a solvent.
  • UV-Vis spectroscopy ultraviolet-visible spectroscopy
  • Figure 4 is a graph showing electrical characteristic curves (output curve and transfer curve) for CNT semiconductor devices according to Examples 1 and 2 and Comparative Example 1.
  • Figure 5 is a graph of the detection test results of the hydrogen gas sensor according to Example 1 for each hydrogen concentration of 0.5 (500 ppb) to 1000 ppm.
  • Figure 6 is a graph showing the results of repeated tests of the hydrogen gas sensor according to Example 1 at a hydrogen gas concentration of 100 ppm in the air.
  • Figure 7 is a graph showing the results of a detection test according to gas type using hydrogen, carbon monoxide, carbon dioxide, ethylene, and methane gas of the hydrogen gas sensor according to Example 1.
  • units used without special mention in this specification are based on weight, and as an example, the unit of % or ratio means weight % or weight ratio, and weight % refers to the amount of any one component of the entire composition unless otherwise defined. It refers to the weight percent occupied in the composition.
  • the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error 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, this includes not only the case where a layer is in contact with another layer, but also the case where one or more other layers exist between the two layers.
  • polymer herein includes polymers and copolymers.
  • copolymer generally refers to any polymer derived from more than one species of monomer, wherein the polymer comprises corresponding repeat units of more than one species. Copolymers are the reaction product of two or more types of monomers and therefore may contain two or more species of corresponding repeat units. Copolymers may exist as block copolymers, random copolymers, and/or alternating copolymers.
  • acrylic in this specification includes both methacrylic and acrylic.
  • acrylate herein includes both methacrylate and acrylate.
  • residue in this specification refers to the remaining 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 polymer surrounds a CNT by electrostatic interaction, and may also include coating, application, bonding, and attachment. Additionally, the electrostatic interaction may mean ⁇ electron interaction ( ⁇ - ⁇ stacking interaction).
  • alkyl in this specification includes both straight chain and branched forms, and may have 1 to 30 carbon atoms, specifically 1 to 20 carbon atoms.
  • halogen and “halo” herein mean fluorine, chlorine, bromine or iodine.
  • haloalkyl refers to an alkyl group in which one or more hydrogen atoms are each replaced with a halogen atom.
  • 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 , -
  • alkenyl herein refers to a saturated straight-chain or branched non-cyclic hydrocarbon containing 2 to 30 carbon atoms, specifically 2 to 20 carbon atoms and at least one carbon-carbon double bond.
  • alkynyl herein refers to a saturated straight-chain or branched non-cyclic hydrocarbon containing 2 to 30 carbon atoms, specifically 2 to 20 carbon atoms and at least one carbon-carbon triple bond.
  • alkoxy in this specification refers to -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 means -O-(alkyl), including (CH 2 ) 5 CH 3 , and the like, where alkyl is as defined above.
  • alkoxycarbonyl radicals include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, etc. It is not limited.
  • cycloalkyl refers to a monocyclic or polycyclic saturated ring having carbon and hydrogen atoms and no carbon-carbon multiple bonds.
  • cycloalkyl groups include, but are not limited to, C 3-10 cycloalkyl (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl). Cycloalkyl groups may be optionally substituted.
  • the cycloalkyl group is a monocyclic or bicyclic ring.
  • aralkyl in this specification refers to alkyl in which one or more hydrogens are replaced with aryl, and includes benzyl, etc.
  • alkylene alkenylene, alkynylene, cycloalkylene, “arylene”, “heteroarylene”, and “alkoxycarbonylene” are respectively “alkyl” and “alkenyl” , “alkynyl”, “cycloalkyl”, “aryl”, “heteroaryl” and “alkoxycarbonyl” refers to a divalent organic radical derived by removal of one hydrogen from said alkyl, alkenyl, alkynyl, cyclo The respective definitions of alkyl, aryl, heteroaryl and alkoxycarbonyl follow.
  • hydroxy means -OH
  • nitro means -NO 2
  • cyano means -CN
  • amino means -NH 2
  • Carboxyl means -COOH
  • carboxylate means -COOM.
  • the M may be an alkali metal or an earth metal.
  • alkali metal in this specification refers to chemical elements other than hydrogen in group 1 of the periodic table, such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
  • alkaline earth metals refer to group 2 elements of the periodic table: beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
  • the present invention relates to a substrate; and a hydrogen gas sensor including a sensing unit, wherein the sensing unit includes a polymer layer formed from a first polymer on the substrate; A composite layer formed from a second polymer-CNT composite on the polymer layer; a metal electrode formed on the composite layer; A palladium nanoparticle layer formed on the composite layer; and a polymer coating layer located on the palladium nanoparticle layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer, and the polymer layer and the composite layer are connected through triazole.
  • the sensing unit includes a polymer layer formed from a first polymer on the substrate; A composite layer formed from a second polymer-CNT composite on the polymer layer; a metal electrode formed on the composite layer; A palladium nanoparticle layer formed on the composite layer; and a polymer coating layer located on the palladium nanoparticle layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer, and
  • the substrate may be an inorganic substrate including glass, quartz, silicon, etc., or polyethylene terephthalate, polyethylene sulfone, polycarbonate, polystyrene, polypropylene, polyester, polyimide, polyetheresterketone, polyesterimide, acrylic resin, and olefin polymer. It may be an organic substrate including a mid copolymer, but is not limited thereto.
  • the substrate may be a typical 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 there are special restrictions if a CNT film can be formed on the substrate. It doesn't work. Additionally, physical or chemical treatment may be performed to improve the adhesion between the substrate and the CNT film.
  • a CNT film may be formed on the substrate to be applied to semiconductor devices, transparent electrodes, displays, etc.
  • the triazole may be represented by the following formula (1).
  • * is each independently a connection point with the first polymer of the polymer layer or the second polymer of the composite layer, and the two * are connection points with different layers.
  • the first polymer is represented by the formula 2 below
  • the second polymer is represented by the formula 3 below
  • the triazole is the first polymer and the second polymer It is formed by a click reaction, and the click reaction can be expressed in Scheme 1 below.
  • P 1 is a residue derived from the first polymer
  • P 2 is a residue derived from the second polymer
  • * is the portion where P 1 is fixed to the substrate
  • 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 of 1 or more.
  • the residue derived from the first polymer refers to the remaining portion of the first polymer excluding the FG 1 functional group, and the first polymer is the same as described later.
  • the residue derived from the second polymer refers to the remaining portion of the second polymer excluding the FG 2 functional group, and the second polymer is the same as described later.
  • the residue derived from the second polymer-CNT complex refers to the remaining portion of the second polymer-CNT complex excluding the FG 2 functional group, and the second polymer-CNT complex is the same as described later.
  • Reaction Scheme 1 If Reaction Scheme 1 is specifically expressed, it may be Reaction Scheme 2 below.
  • the alkynyl functional group of Chemical Formula 2 and the azide functional group of Chemical Formula 3 can form a triazole ring through a click reaction in the presence of a copper catalyst.
  • P 1 and P 2 (CNT) By chemically bonding P 1 and P 2 (CNT) through the triazole ring, a polymer layer and a composite layer can be formed on the substrate.
  • the type of the first polymer is not particularly limited if it has an alkynyl functional group
  • the type of the second polymer is not particularly limited if it has an azide functional group.
  • the first polymer can be broadly divided into types as long as it has hydroxy, epoxy, carboxyl, thiol, alkene and alkynyl, specifically epoxy and alkynyl functional groups in the side chain. It can be used without restrictions.
  • the first polymer may be an acrylic copolymer, the acrylic copolymer may be a polymerization of two or more types of monomers, and the monomer may be an acrylic monomer or a methacrylic monomer.
  • the monomer may have hydroxy, epoxy, carboxyl, thiol, alkene, and alkynyl functional groups at the terminal, and may specifically have epoxy and alkynyl functional groups.
  • the monomer can be directly synthesized and used, or a commercially available product can be used, but is not limited thereto.
  • the acrylic copolymer may be synthesized by a commonly used polymerization method. Specifically, it may be solution polymerization, but is not limited thereto.
  • the solution polymerization may be polymerized including the monomer, initiator, and solvent.
  • the initiator and solvent are not particularly limited as long as they are commonly used, but specifically, azobisisobutyronitrile (AIBN) may be used as the initiator.
  • the solvent may be dimethylformamide (DMF). Additionally, the content is not particularly limited as long as it does not impair the physical properties described in the present invention.
  • the first polymer may have a number average molecular weight (Mn) of 5,000 to 100,000 Da, specifically 10,000 to 60,000 Da, and more specifically 10,000 to 30,000 Da, but is not limited thereto.
  • Mn number average molecular weight
  • the number average molecular weight can be adjusted by the monomer content ratio and polymerization conditions.
  • the first polymer or Formula 2 may be a copolymer 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 monomers having a FG 1 functional group at the terminal
  • z and k are independently integers of 1 to 7
  • a 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, specifically 0.5 to 5:1, and more specifically 0.8 to 2:1. It may satisfy, but is not particularly limited thereto.
  • the alkynyl functional group may click-react with the azide functional group of Formula 3 to form a triazole ring.
  • p 1 to p 2 are repeating units derived from monomers having a FG 1 functional group at the terminal, and specifically, the monomer is not greatly limited as long as it is a monomer capable of condensation polymerization or addition polymerization, but specifically, it is an acrylic type capable of radical polymerization. , it may be one or more monomers selected from methacryl-based, vinyl-based, etc.
  • a and b may refer to the number of moles of each p 1 and p 2 repeating unit in the first polymer.
  • the ratio of a and b (a:b) can be adjusted by adjusting the molar ratio of monomers corresponding to the p 1 and p 2 repeating units or by adjusting the polymerization conditions, but is not limited to this.
  • the first polymer or 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 a combination thereof.
  • 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 ) may be substituted with one or more selected from alkyl, C 6-30 aryl, and C 3-30 heteroaryl, z and k are integers of 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 or 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 ) may be substituted with one or more selected from alkyl and C 6-20 aryl, z and k are integers of 1 to 3, and a and b are 0.1 to 10:1, specifically 0.5 to 5: It may satisfy 1.
  • the first polymer or Chemical Formula 6 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 of 1 or more. Specifically, R 2 to R 3 may independently be C 1-3 alkylene, more specifically R 2 to R 3 may be methylene, and a and b may specifically satisfy 0.8 to 2:1. there is.
  • z and k in Formula 4 refer to the number of FG 1 included in the 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 a FG 1 functional group at the terminal
  • p 3 is a FG 3 functional group at the terminal. It is a repeating unit derived from a monomer having, z, k, and t are independently integers of 1 to 7, and a, b, and c are integers of 1 or more.
  • z, k, and t may independently be integers of 1 to 3, and 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 to this.
  • the epoxy functional group may react chemically with the substrate, and the alkynyl functional group may click-react with the azide functional group of Formula 3 to form a triazole ring.
  • p 1 to p 2 may be a repeating unit derived from a monomer having a 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 monomer may be a condensation There is no significant limitation as long as it is a monomer capable of polymerization or addition polymerization, but specifically, it may be one or more monomers selected from acrylic-based, methacrylic-based, and vinyl-based monomers capable of radical polymerization.
  • a to c may refer to the number of moles of p 1 to p 3 repeating units in the first polymer.
  • the ratio of a to c can be adjusted by adjusting the input 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 to this.
  • the first polymer or 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 It is a combination of, and 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 ) 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, and z, k and t are 1 to 7 is an
  • 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 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 ) 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
  • 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.
  • the first polymer or 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, and a, b and c are integers of 1 or more. Specifically, R 2 to R 4 are independently C 1-3 alkylene, and 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 refer to the number of FG 1 and FG 3 included in the 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 refer to repeating units constituting the first polymer of Chemical Formula 2.
  • the p 1 and p 2 repeating units may be independently derived from monomers containing one or more FG 1 functional groups at the terminals, and the p 3 repeating units in Formula 5 may have one or more FG 3 functional groups at the terminals. It may be derived from a monomer containing a functional group.
  • 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 greatly limited as long as it can be copolymerized.
  • the type is particularly limited as long as it is a monomer capable of condensation polymerization or addition polymerization. It doesn't work. Specifically, it may include monomers capable of radical polymerization such as acrylic, methacrylic, and vinyl monomers, but is not limited thereto.
  • the ratio of a and b in Formula 4 can be adjusted by adjusting the molar ratio of the monomers added to the polymerization, and the ratio of a to c in Formula 5 can be adjusted. That is, the molar ratio of the corresponding monomers added to the polymerization and the ratio of the repeating units p 1 to p 3 may be similar or identical. Specifically, the number of moles of the 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, and the monomers corresponding to each p 1 to p 3 are added at a molar ratio of 2: 2: 1. When polymerized, a:b:c may be the same 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 in the 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 end and is CNT. If you can wrap it, you can use it without any particular restrictions.
  • the second polymer can be used to produce a second polymer-CNT composite by wrapping CNTs, and may specifically be a fluorene-based copolymer.
  • the fluorene-based copolymer may be a copolymerization of two or more types of fluorene-based monomers.
  • the second polymer is a fluorene-based copolymer, which is an electrically conductive conjugated polymer, CNTs can be wrapped more effectively, and thus a film with high-density CNTs can be manufactured, and this can be used to produce CNTs with excellent electrical properties.
  • Semiconductor devices and hydrogen gas sensors can be manufactured.
  • the second polymer or the compound represented by Formula 3 may be a copolymer that simultaneously includes a repeating unit (n) of Formula 10 below and a repeating unit (m) of 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. Specifically, R 6 to R 7 may independently be C 5-20 alkylene, and R 8 to R 9 may independently be C 5-20 alkyl.
  • CNTs can be effectively wrapped through ⁇ -electron interaction ( ⁇ - ⁇ stacking interaction) with the CNT sidewall.
  • a second polymer-CNT composite can be prepared by selectively wrapping the sc-SWCNT and using this to form a composite layer.
  • the number average molecular weight of the copolymer containing 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 There is no limitation thereto as long as it does not impair the intended physical properties.
  • the copolymer containing the repeating unit (n) and the repeating unit (m) may be a random copolymer in which each repeating unit is randomly polymerized, or it may be an alternating copolymer in which each repeating unit is crossed and bonded. And specifically, 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 containing the repeating unit (n) and the repeating unit (m) may have further improved selectivity for sc-SWCNT, and as a result, a CNT film with a higher density of sc-SWCNT can be coated.
  • the hydrogen gas sensor coated with the high-density sc-SWCNT it is good to realize further improved sensitivity and selectivity.
  • the mole fraction can be used without major limitations as long as 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 second polymer or a copolymer containing 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 may independently be C 5-20 alkylene
  • R 8 , R 9 , R 18 and R 19 may independently be C 5-20 alkyl
  • 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 greatly limited, but may be 0.0001 or more, provided that the physical properties targeted by the present invention are not impaired. Not limited.
  • the copolymer may be a random copolymer in which each repeating unit is randomly polymerized, or it may be an alternating copolymer in which each repeating unit is crossed and bonded, and specifically, it may be a random copolymer.
  • the hydrogen gas sensor 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 contains a material that easily reacts with the surface of the substrate layer, such as a silane coupling agent, and a photopolymerization initiator that can effectively absorb energy and form radicals to cause a crosslinking reaction, such as a benzophenone structure. It may be a unit derived from a compound.
  • the self-assembled monolayer (SAM) of the hydrogen gas sensor 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 It is -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 specifically, Formula 12 may be represented by Formula 13 below.
  • the compounds represented by Formulas 12 and 13 include a benzophenone structure and can effectively absorb an energy beam and react with the alkyl chain of the polymer in contact with the electrons of the n-orbital of the carbonyl group of benzophenone. Accordingly, the compounds represented by Formulas 12 and 13 and the first polymer may be crosslinked by irradiation with an energy beam.
  • the energy beam may be ultraviolet (UV) light.
  • 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 simultaneously cross-linked with the first polymer, thereby forming a polymer formed from the first polymer on the substrate.
  • the metal electrode of the hydrogen gas sensor is for measuring changes in resistance or current and may include a source electrode and a drain electrode spaced apart from each other on the composite layer.
  • the metal electrode is one or more 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 SnO2), GZO (Ga-doped ZnO), ZTO (zinc tin oxide), GIO (gallium indium oxide), ZnO, Pd, Ag and their It may be an electrode formed by one or more elements selected from the group consisting of combinations.
  • the thickness of the metal electrode may be 5 to 100 nm, preferably 20 to 80 nm, but is not limited thereto.
  • the palladium nanoparticle layer of the hydrogen gas sensor is a sensing unit that detects hydrogen, and may be located in an area where the source electrode and the drain electrode are spaced apart, and hydrogen gas can be sensed by the palladium nanoparticle layer. do. Specifically, when hydrogen is exposed to the palladium nanoparticle layer while power is supplied to the metal electrode, hydrogen is adsorbed and electrical characteristics change, allowing hydrogen to be detected.
  • the palladium nanoparticle layer of the hydrogen gas sensor according to an embodiment of the present invention may be formed to have a thickness of 1 to 20 nm, specifically 2 to 10 nm.
  • the palladium nanoparticle layer may be made of palladium nanoparticles in the form of clusters or dispersed particles. As a specific example, it may be made of cluster-type palladium nanoparticles with an average particle diameter of 0.1 to 10 nm, preferably 0.5 to 5 nm.
  • This palladium nanoparticle layer has excellent conductivity and hydrogen adsorption performance at the same time, allowing it to adsorb a large amount of hydrogen gas and enable highly sensitive sensing.
  • the palladium nanoparticle layer is located in a specific area, that is, an area where the source electrode and the drain electrode are spaced apart.
  • the palladium nanoparticles may be distributed uniformly or non-uniformly in the area.
  • the palladium nanoparticles are distributed only in a partial area on the surface of the composite layer in the area where the source electrode and drain electrode are spaced apart, and the source electrode and the drain electrode
  • the surface of the composite layer in the area where the drain electrodes are spaced apart may include a first area where the palladium nanoparticle layer is located and a second area where the palladium nanoparticle layer is not located.
  • the area of the second region may be 50% to 90%, preferably 60% to 80%, of the total area of the surface of the composite layer partitioned by the source electrode and the drain electrode.
  • the hydrogen gas sensor including the palladium nanoparticle layer composite layer as described above not only provides high sensitivity sensing, but also provides highly sensitive sensing of hydrogen gas even under various environmental conditions, specifically at a temperature of -50°C to 300°C and humidity of 10 to 80%. Sensing may be possible.
  • the polymer coating layer of the hydrogen gas sensor according to an embodiment of the present invention allows hydrogen gas to selectively pass through, enabling more highly sensitive hydrogen gas sensing. Furthermore, the polymer coating layer plays a role in protecting the sensing unit by preventing the palladium nanoparticles from escaping from external environments such as moisture and air, and prevents hydrogen gas sensitivity from being reduced due to moisture, etc. when exposed to the outside for a long period of time. In other words, the polymer coating layer can significantly improve the sensitivity, hydrogen selectivity, and physical and chemical stability of the sensing unit. Specifically, the polymer coating layer may include an acrylate-based polymer.
  • the thickness of the polymer coating layer is not particularly limited as long as it can sufficiently protect the palladium nanoparticle layer, but may be 100 nm or more, or 500 nm or more, specifically 1 ⁇ m to 10 ⁇ m, but is not limited thereto.
  • the polymer coating layer may be formed to be thicker than the thickness of the electrode, so that the edge of the polymer coating layer may be located on the electrode. Such a polymer coating layer can serve to further increase the durability of the hydrogen gas sensor by protecting the electrodes of the hydrogen gas sensor from the external environment.
  • the polymer coating layer of the hydrogen gas sensor includes an acrylate-based polymer.
  • the weight average molecular weight of the acrylate-based polymer may be 1,000 to 1,000,000 g/mol, and the specific It may be 5,000 to 500,000 g/mol, more specifically 20,000 to 400,000 g/mol.
  • the acrylate-based polymer may include poly(C 1-4 )alkyl methacrylate, specifically, polymethacrylate, polymethylacrylate, polymethyl methacrylate ( It may include one or more selected from PMMA), polyethylacrylate, polyethylmethacrylate, or mixtures thereof.
  • the polymer coating layer may include polymethyl methacrylate, and at the same time, it may be advantageous in improving the selectivity of hydrogen gas by having a non-porous structure.
  • a polymer coating layer containing non-porous polymethyl methacrylate is desirable because it can have excellent hydrogen gas selectivity, high sensitivity, and high reliability in hydrogen gas sensing.
  • non-porous means that no pores are observed with the naked eye when observing the surface of the polymer coating layer in a 25 ⁇ m ⁇ 20 ⁇ m photograph measured with a scanning electron microscope. Specifically, this may mean that pores with a diameter of about 10 nm or more are not found.
  • the method of detecting hydrogen gas of the present invention through a CNT-based hydrogen gas sensor can be accomplished by measuring current or resistance before and after exposing the detection target gas to the sensor. For example, setting a standard by measuring the drain current (Ids(ref)) of a hydrogen gas sensor; introducing a gas to be detected between the source electrode and the drain electrode; A detection step of measuring the drain current (Ids(detect)) when the detection target gas is introduced; and analyzing the concentration of the detection gas using the measured drain current value.
  • the detection gas may be detected based on the drain current value changed (increased) before and after introduction of the detection target gas.
  • detection of the detection gas may be performed by measuring the changed resistance value rather than the drain current value changed before and after the introduction of the detection target gas.
  • the operating (detection) temperature of the hydrogen gas sensor may be in the range of -50 to 300 °C, specifically -10 to 200 °C, more specifically 4 to 100 °C, and this method of detecting hydrogen gas is 0.1 to 100000 ppm, specifically 1 It can detect hydrogen gas having a concentration range of 80,000 ppm, and the CNT-based hydrogen gas sensor according to an embodiment of the present invention can sense hydrogen gas with high sensitivity even at a low concentration of 200 ppm or less.
  • the present invention relates to a substrate; and a hydrogen gas sensor including a sensing unit, wherein the sensing unit includes a polymer layer formed from a first polymer on the substrate; A composite layer formed from a second polymer-CNT composite on the polymer layer; a metal electrode formed on the composite layer; A palladium nanoparticle layer formed on the composite layer; and a polymer coating layer located on the palladium nanoparticle layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer, and the polymer layer and the composite layer are connected through triazole.
  • a method of manufacturing a hydrogen gas sensor can be provided.
  • the method for manufacturing a hydrogen gas sensor according to an embodiment of the present invention is
  • the first polymer may be represented by Formula 2
  • the second polymer may be represented by Formula 3
  • the first polymer and the second polymer may be represented by Formula 3. 2
  • the specific description of the polymer is the same as described above.
  • 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 compound unfixed to the substrate with a solvent.
  • SAM self-assembled monolayer
  • the step (a-1) of 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, Organic solvents or mixtures thereof can 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, methanol, DMF, and toluene, or a mixture thereof, preferably sulfuric acid.
  • the step (a-2) of coating the self-assembled monolayer may be performed by spin coating, dip coating, gas phase deposition, doctor blade coating, and curtain coating methods. .
  • it may be a dip coating method, and the dip coating method may include immersing the cleaned substrate in a self-assembled monolayer solution for 1 to 20 hours, preferably for 3 to 10 hours. .
  • the immersion process may be washed with one or more solvents selected from the group consisting of acetone, methanol, ethanol, isopropyl alcohol (IPA), toluene, and tetrahydrofuran (THF), preferably ethanol.
  • solvents selected from the group consisting of acetone, methanol, ethanol, isopropyl alcohol (IPA), toluene, and tetrahydrofuran (THF), preferably ethanol.
  • This may be a first wash with toluene and a second wash with toluene.
  • Whether the self-assembled monomolecular layer 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 monomolecular layer is coated.
  • the self-assembled monomolecular layer solution may include a compound represented by Formula 12 and a solvent, and the self-assembled monomolecular layer solution may include the compound represented by Formula 12.
  • the concentration may preferably be 0.001 to 3 M, but is not particularly limited.
  • Chemical Formula 12 may be represented by Chemical Formula 13, and the descriptions of Chemical Formulas 12 and 13 are the same as those 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.
  • the solvent may 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 preferably toluene, but the formula (12) There is no particular limitation as long as the solvent does not react with the compound represented by .
  • the step (a-3) of coating the first polymer includes spin coating, dip coating, dropping, spray coating, solution casting, and bar coating. It may be coated by a method selected from coating, roll coating, and gravure coating, and preferably, it may be selected from spin coating, spray coating, solution casting, and roll coating. Additionally, coating may be performed by preparing a coating solution containing the first polymer.
  • the coating liquid 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), toluene, acetone, 1 , one selected from 1,4,-Dioxane, dimethylacetamide (DMA, N,N-dimethylacetamide), dimethylformamide (DMF), tetrahydrofuran (THF), and chloroform. It may be more than 1,4-dioxane or chloroform.
  • the coating solution may contain 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 the desired coating thickness. By preparing a coating solution containing the first polymer, an appropriate method can be selected among the above methods depending on the characteristics of the coating solution and the intended use.
  • the first polymer may be represented by the formula 2, and specifically, the formula 2 is represented by the formula 4. You can. Specifically, Formula 4 may be represented by Formula 6, and Formula 6 may be represented by Formula 7. The description of Chemical Formulas 2, 4, 6, and 7 is the same as previously described.
  • the UV curing step (a-4) involves crosslinking the compound represented by Formula 12 and the first polymer to immobilize the polymer layer formed from the first polymer on the substrate. This can be performed to manufacture a hydrogen gas sensor that is stable in water and organic solvents and has excellent inter-device reproducibility by uniformly coating the CNT film on the substrate layer at high density.
  • the UV curing time may be from 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/cm2, but is not limited thereto.
  • 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 it is a solvent in which the unreacted compound is dissolved. Non-limiting examples include toluene, acetone, 1,4-dioxane, EA, DMA, DMF, and THF. and one or more solvents selected from chloroform, etc. may be used.
  • 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 (a'-1) of washing the substrate with a solvent is performed to remove unreacted organic and inorganic substances remaining on the substrate, and the solvent is Commonly used inorganic solvents, organic solvents, or mixtures thereof can be used. Examples of specific compounds may be the same as or different from the solvent used in the step of washing the substrate with solvent (a-1).
  • step (a'-2) of coating the first polymer may be performed in the same manner as step (a-3) of coating the first polymer.
  • the first polymer may be represented by the formula 2, and specifically, the first polymer or the formula 2 is It may be represented by Chemical Formula 5. Specifically, the first polymer or Formula 5 may be represented by Formula 8, and more specifically, the first polymer or Formula 8 may be represented by Formula 9. The description of Chemical Formulas 2, 5, 8, and 9 is the same as previously described.
  • the heat treatment step (a'-3) may be a process in which 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 depending on the thickness of the polymer layer, etc., and if the temperature does not impair the physical properties targeted by the present invention, and the time range 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 it is a solvent in which the unreacted compound is dissolved. Non-limiting examples include toluene, acetone, 1,4-dioxane, EA, DMA, DMF, and THF. and one or more solvents selected from chloroform, etc. may be used.
  • the second polymer-CNT composite solution according to an embodiment of the present invention may include a second polymer, CNTs, and a solvent.
  • the second polymer-CNT composite solution may be a solution in which a second polymer obtained by wrapping CNTs is dissolved in a solvent.
  • the CNTs include single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes, multi-walled carbon nanotubes (Multi-walled carbon nanotubes), and bundled carbon nanotubes (Rope). It may be one or more selected from the group consisting of carbon nanotubes, or it may be single-walled carbon nanotubes (SWCNTs). Preferably, it may be conductive single-walled carbon nanotubes (m-SWCNT), semiconducting single-walled carbon nanotubes (sc-SWCNT), or a mixture thereof. When semiconducting single-walled carbon nanotubes (sc-SWCNT) are used, , it may be desirable to manufacture semiconductor devices and hydrogen gas sensors with better electrical performance.
  • CNTs with appropriate properties can be selected to form a CNT film on the base substrate.
  • 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 it does not affect dispersibility 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).
  • aromatic hydrocarbon solvents such as benzene, toluene, and xylene
  • aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, and methylcyclohexane (MCH).
  • Toluene or methylcyclohexane can be used.
  • Polar solvents such as chloroform or tetrahydrofuran (THF) may
  • the method for producing a second polymer-CNT composite solution 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 included at a concentration of 0.05 to 5 mg/ml. You can.
  • the second polymer is preferably completely dissolved in the solvent, and may be dissolved in a temperature range of 50 to 100°C.
  • the second polymer (second polymer-CNT composite) wrapping the carbon nanotubes may be separated through centrifugation, and then manufactured through a filtration process and redispersion process, but is not limited to this.
  • the concentration of the second polymer-CNT complex in the second polymer-CNT complex solution after the redispersion process may be 0.001 to 10 mg/ml, and the density of the CNT film is adjusted by adjusting the concentration. It may be, but is not limited to this.
  • the solvent used in the redispersion process may be the same as or different from the specific example 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.
  • a substrate is manufactured with a second polymer-CNT composite solution that satisfies the above range, a CNT film of appropriate density can be formed on the substrate layer, and the high-stability and high-density CNT film targeted by the present invention can be manufactured. Even better, the prepared second polymer-CNT composite solution can be used in the step (b) of immersing the coated substrate in the second polymer-CNT composite solution.
  • the second polymer may be a copolymer simultaneously containing the repeating unit (n) of Formula 10 and the repeating unit (m) of Formula 11, and the description of the copolymer was given above. It is the same as described.
  • the step (c) of forming a polymer layer and a composite layer by clicking reaction of the first polymer and the second polymer is performed through heating or ultrasonic treatment under a copper catalyst. It may be something that is going on.
  • step (c) 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.
  • ultrasonic treatment may be performed 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 hours.
  • the temperature, intensity and time are not particularly limited as long as they do not impair the physical properties targeted by the present invention.
  • the reaction can be carried out by variously adjusting the time to achieve the desired CNT film density.
  • the density of the CNT film can be confirmed by observing the surface of the coating layer through Raman spectroscopy, scanning electron microscopy (SEM), or optical microscopy.
  • a high-density CNT film when manufacturing a hydrogen gas sensor through the click reaction, can be uniformly coated in a short time, so not only is the work easy and efficient, but the CNT film is chemically bonded. By being coated on the substrate layer, it has excellent adhesion and stability against water and organic solvents, so the CNT film does not peel off even after washing. In addition, when using the click reaction, the CNT film is uniformly coated, improving reliability. It is good to be able to manufacture a hydrogen gas sensor with excellent sensitivity and selectivity even at low hydrogen gas concentrations.
  • a step of washing unreacted compounds with an organic solvent may be performed, which may include removing the catalyst, monomer and This may be done to manufacture a high-purity CNT film by removing unreacted compounds such as polymers.
  • the organic solvent may be any commonly used solvent without particular limitation, and non-limiting examples include one or more solvents selected from toluene, acetone, 1,4-dioxane, EA, DMA, DMF, THF, and chloroform. there is.
  • the cleaning process may be performed through ultrasonic cleaning, and the ultrasonic intensity may be strong at 170 to 230 W.
  • the CNT-based hydrogen gas sensor according to the present invention is very good because it can maintain a high-density CNT film even after multiple ultrasonic cleaning processes and ensure stability against water and organic solvents.
  • the step (d) of forming a source electrode and a drain electrode on the composite layer may be performed using a known or conventional electrode forming method.
  • 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 the source electrode and drain electrode using a shadow mask may be used.
  • the shadow mask may be a metal shadow mask, a polymer shadow mask such as PDMS or PMMA, etc.
  • Detailed descriptions of the source electrode and drain electrode and examples of compounds are the same as described above and are therefore omitted.
  • step (e) is a step of forming a palladium nanoparticle layer in an area where the source electrode and the drain electrode are spaced apart, including physical or chemical vapor deposition of palladium nanoparticles, For example, it can be performed through sputtering, thermal evaporation, electron beam evaporation, electroplating, and spraying an aqueous metal solution on the sample surface. Specifically, it is performed by thermal evaporation at a temperature lower than the melting point of palladium nanoparticles. You can.
  • the temperature conditions may be 80 to 500°C, preferably 100 to 400°C.
  • step (f) is a step of dissolving a polymer in a solvent and then coating and drying the palladium nanoparticle layer to form a polymer coating layer
  • the coating method Can be performed according to a commonly used or known method, for example, may be performed according to any one method selected from spin coating, spray coating, knife coating, and roll coating, but is not limited thereto.
  • PMMA polymethyl methacrylate
  • a polymer coating layer can be formed by coating a solution in which the polymer is dissolved in a solvent and then drying the solution by evaporating the solvent.
  • the drying is not limited as long as the temperature conditions are capable of evaporating the solvent, but may be performed at a temperature of 100 to 300°C, specifically 120 to 200°C.
  • Detailed descriptions of the polymer coating layer and examples of compounds are the same as described above, so they are omitted.
  • the solution in which the polymer is dissolved may contain the polymer at a concentration of 0.1 to 50 mg/mL, preferably 1 to 10 mg/mL, and more preferably 2 to 8 mg/mL, but is not limited thereto.
  • the concentration can be easily adjusted depending on the thickness of the target polymer coating layer.
  • the solvent may be a halogenated alkoxy benzene compound, and the halogen may be chlorine, fluorine, or bromine.
  • the halogenated alkoxy benzene compound may be a chlorinated (C 1-4 ) alkoxy benzene compound, and specifically may be anisole.
  • the polymer coating layer produced using such a solvent can have a non-porous surface and can effectively achieve improved selectivity for hydrogen gas.
  • an acrylate copolymer represented by the following formula (6) can be provided.
  • Formula 6 is the same as described above, and Formula 6 may be represented by the following compound, but is not limited thereto.
  • an acrylate copolymer represented by the following formula (8) can be provided.
  • Formula 8 is the same as described above, and Formula 8 may be represented by the following compound, but is not limited thereto.
  • Ar may be two identical R 1s connected to each other, or two different R 1s may be connected to each other.
  • the R 1 may include z numbers of FG 1 , and when two different R 1s are connected to the Ar, z of each 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 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 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 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 n was about 0.1.
  • the fluorene-based copolymer (iii) of Preparation Example 4 was added to 20 ml of methylcyclohexane (MCH) at a concentration of 1 mg/ml 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, dispersed at room temperature using an ultrasonicator (Sonics & Materials Inc., VCX-750, 750W), and centrifuged (Hanil Scientific Inc.). , Supra R30) was 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 fluorene-based copolymer (iii) wrapping sc-SWCNTs.
  • the obtained pellet was washed several times, then 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.
  • the 100 nm SiO 2 /Si substrate layer (Chung King Enterprises) was thoroughly washed with a 7:3 solution of sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ), and then washed again with water and toluene. After washing, the solvent was completely removed through nitrogen gas and heat treatment at 110°C for 10 minutes.
  • the dried substrate layer was immersed in the BPS solution of Preparation Example 8 and left for 12 hours, then washed in ethanol and toluene for 3 minutes each using an ultrasonic cleaner, and coated with a self-assembled monolayer (SAM).
  • SAM self-assembled monolayer
  • a solution of the acrylate copolymer (i) of Preparation Example 2 dissolved in 1,4-dioxane at a concentration of 5 mg/ml was spin-coated on the SAM-coated substrate layer at 1000 rpm for 50 seconds, and 727 mJ/ml.
  • the substrate fixation step was performed by UV curing for 1 minute at an intensity of cm2.
  • the compound unfixed to the substrate layer was removed by ultrasonic washing in chloroform for 1 hour, the solvent was removed with nitrogen gas, and heat treatment was performed at 100°C for 10 minutes.
  • the self-assembled monolayer (SAM) coating was confirmed by confirming that the contact angle measurement result for water was 70° or more, as shown in (a) of Figure 3.
  • SAM self-assembled monolayer
  • the substrate layer coated with the acrylate copolymer (i) was placed in a vial and immersed in 1 ml of the second polymer-CNT composite solution of Preparation Example 7, followed by 0.003 g of copper sulfate (CuSO 4 ) and sodium ascorbate. ) 0.019 g and 0.5 ml of distilled water were added and nitrogen purged.
  • the vial was immersed in an ultrasonic cleaner and sonicated at a temperature of 50°C and an intensity of 110W for 5 minutes to perform a click reaction. After completion of the reaction, the substrate was ultrasonic washed in toluene to remove unreacted compounds, the solvent was removed with nitrogen gas, and the substrate was heat treated at 150°C for 30 minutes.
  • a CNT semiconductor device was manufactured by depositing Ti to a thickness of 5nm and Au to a thickness of 60nm and a separation distance of 200 ⁇ m using a shadow mask on a completely dried substrate to form source and drain electrodes.
  • the electrical characteristic curve (output curve and transfer curve) of the manufactured CNT semiconductor device was measured and shown in Figure 4 (a).
  • Pd was deposited on the CNT semiconductor device using a thermal evaporator at a speed of 0.1 ⁇ /s to form a palladium nanoparticle layer with an average thickness of 3 nm.
  • 4 mg/ml of PMMA (solvent anisole) was spin-coated (2000 rpm, 30 seconds) and then heat treated at 175°C for 10 minutes to form a PMMA coating layer, ultimately manufacturing a hydrogen gas sensor.
  • the 100 nm SiO 2 /Si substrate layer (Chung King Enterprises) was thoroughly washed with a 7:3 solution of sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ), and then washed again with water and toluene. After washing, the solvent was completely removed through nitrogen gas and heat treatment at 110°C for 10 minutes.
  • a solution of the acrylate copolymer (ii) of Preparation Example 3 dissolved in 1,4-dioxane at a concentration of 5 mg/ml was spin-coated on the dried substrate layer at 1000 rpm for 50 seconds, and 2 times at 110°C.
  • the substrate fixation step was performed by heat treatment for a period of time.
  • the compound unfixed to the substrate layer was removed by ultrasonic washing in chloroform for 1 hour, the solvent was removed with nitrogen gas, and heat treatment was performed at 100°C for 10 minutes.
  • the acrylate copolymer (ii) solution was coated and heat cured through UV-Vis spectroscopy, and then before and after washing the substrate layer with chloroform. The results were compared.
  • the substrate layer coated with the acrylate copolymer (ii) was placed in a vial and immersed in 1 ml of the second polymer-CNT composite solution of Preparation Example 7, followed by 0.003 g of copper sulfate (CuSO4) and sodium ascorbate. Nitrogen purge was performed by adding 0.019 g and 0.5 ml of distilled water. The vial was immersed in an ultrasonic cleaner and sonicated at a temperature of 50°C and an intensity of 110W for 5 minutes to perform a click reaction. The subsequent steps were performed in the same manner as in Example 1, and finally, the CNT semiconductor device and hydrogen gas sensor according to Example 2 were manufactured. The shadow mask used was the same as that used in Example 1, and the electrical characteristic curves (output curve and transfer curve) for the CNT semiconductor device manufactured according to Example 2 are shown in Figure 4 (b). ) is shown in.
  • the second polymer-CNT composite solution of Preparation Example 7 was spin-coated on the substrate layer coated with the acrylate copolymer (i) in Example 1 under conditions of 2000 rpm, not using a click reaction, and dried on a hot plate. The above process was repeated twice, and after film coating, the substrate was ultrasonic washed in toluene to remove unreacted compounds, and the solvent was removed with nitrogen gas, followed by heat treatment at 150°C for 30 minutes.
  • a CNT semiconductor device according to Comparative Example 1 was formed by depositing Ti to a thickness of 5 nm and Au to a thickness of 60 nm and a separation distance of 200 ⁇ m using a shadow mask on a completely dried substrate to form a source electrode and a drain electrode. Manufactured. Electrical characteristic curves (output curve and transfer curve) for all elements of the hydrogen gas sensor according to Comparative Example 1 are shown in FIG. 4(c).
  • Figure 5 shows the detection test results of the hydrogen gas sensor according to Example 1 at hydrogen concentrations of 0.5 (500 ppb) to 1000 ppm
  • Figure 6 shows the results of repeated tests at a hydrogen concentration of 100 ppm in the air
  • Figure 7 shows the results of hydrogen, carbon monoxide, carbon dioxide, ethylene, and methane gas detection tests.
  • the hydrogen gas sensor according to Example 1 of the present invention showed a sensitive current change even at low concentrations, specifically hydrogen gas concentrations of 500 ppb or more, and furthermore, even in repeated tests in Figure 6, a constant change was observed. It was confirmed that reliability could be easily secured by presenting the results.
  • the CNT-based hydrogen gas sensor according to the present invention exhibits excellent selectivity and high sensitivity to hydrogen gas in that it reacts selectively to hydrogen gas over other gases.
  • the hydrogen gas sensor according to Example 2 also showed sensitivity and selectivity equivalent to Example 1.
  • the hydrogen gas sensor according to Comparative Example 1 showed no change in current at a hydrogen gas concentration of 500ppb or more, and when tested repeatedly, it showed different result values, making it difficult to secure reproducibility and reliability.
  • the hydrogen gas sensor according to the present invention has the advantage of being stable in water and organic solvents as the CNTs rarely peel off even if the cleaning process is performed several times, and at the same time, reproducibility between devices can be easily secured.
  • a hydrogen gas sensor was manufactured using a click reaction to solve the problems of the conventional CNT-based hydrogen gas sensor, which is easily peeled off, vulnerable to organic solvents, and has poor reliability between devices.

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Abstract

La présente invention permet : de fabriquer un substrat revêtu de CNT, qui comporte un film de CNT hautement dense et uniforme formé sur ce dernier et présente ainsi une stabilité élevée contre l'eau ou un solvant organique, à l'aide d'une réaction click ; et de fabriquer un capteur de gaz hydrogène présentant une excellente fiabilité et une excellente sensibilité à l'aide de ce dernier. En particulier, contrairement aux approches classiques impliquant un revêtement par pulvérisation et un revêtement par centrifugation d'une solution de CNT dans lesquelles la reproductibilité et la fiabilité ne pouvaient pas être obtenues en raison de différences significatives de propriétés physiques entre les dispositifs, la présente invention permet de fabriquer un capteur de gaz hydrogène présentant une excellente sélectivité et une excellente sensibilité gaz hydrogène, tout en présentant également une reproductibilité et une fiabilité élevées, à l'aide d'un procédé relativement simple.
PCT/KR2023/004256 2022-03-30 2023-03-30 Film de cnt utilisant une réaction click, capteur de gaz hydrogène à base de cnt l'utilisant, et son procédé de fabrication WO2023191534A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050039016A (ko) * 2003-10-23 2005-04-29 한국화학연구원 팔라듐이 코팅된 탄소 나노튜브 수소센서
KR20130125183A (ko) * 2012-05-08 2013-11-18 연세대학교 산학협력단 수소 센서 및 수소 센서 제조방법
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
KR100990815B1 (ko) * 2008-07-07 2010-10-29 재단법인서울대학교산학협력재단 수소센서 및 그 제조방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050039016A (ko) * 2003-10-23 2005-04-29 한국화학연구원 팔라듐이 코팅된 탄소 나노튜브 수소센서
KR20130125183A (ko) * 2012-05-08 2013-11-18 연세대학교 산학협력단 수소 센서 및 수소 센서 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, AMERICAN CHEMICAL SOCIETY, vol. 127, no. 41, 1 October 2005 (2005-10-01), pages 14518 - 14524, XP055092760, ISSN: 00027863, DOI: 10.1021/ja054958b *
JI XIAOLI, GUANG SHANYI, XU HONGYAO, KE FUYOU, QIN XIAOYUN: "Fluorene‐based click polymers: Relationship between molecular structure and nonlinear optical properties", JOURNAL OF APPLIED POLYMER SCIENCE, JOHN WILEY & SONS, INC., US, vol. 131, no. 19, 5 October 2014 (2014-10-05), US , XP093092751, ISSN: 0021-8995, DOI: 10.1002/app.40878 *

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