WO2023191535A1 - Substrat à motifs, revêtu d'un film de cnt, utilisant une réaction click et procédé de fabrication associé - Google Patents

Substrat à motifs, revêtu d'un film de cnt, utilisant une réaction click et procédé de fabrication associé Download PDF

Info

Publication number
WO2023191535A1
WO2023191535A1 PCT/KR2023/004257 KR2023004257W WO2023191535A1 WO 2023191535 A1 WO2023191535 A1 WO 2023191535A1 KR 2023004257 W KR2023004257 W KR 2023004257W WO 2023191535 A1 WO2023191535 A1 WO 2023191535A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
formula
patterned
cnt
coated substrate
Prior art date
Application number
PCT/KR2023/004257
Other languages
English (en)
Korean (ko)
Inventor
임보규
박종목
정서현
정유진
김예진
전승주
김가영
이혜민
Original Assignee
한국화학연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2023191535A1 publication Critical patent/WO2023191535A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • 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
    • C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
    • 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

Definitions

  • the present invention relates to a patterned CNT film coated substrate using a click reaction and a method for manufacturing the same. Specifically, it has excellent stability against water or organic solvents and can pattern a CNT film in a simple process through exposure and click reaction. It relates to a manufactured patterned CNT film coated substrate and its manufacturing method.
  • Carbon nanotube (CNT) thin film refers to a nanofilm with a thickness of 100 nm or less, has light transparency, and can be applied to field emitted displays as a conductor, and can be used when CNTs are uniaxially oriented at high density. In addition, when patterned, it can be widely used in electronic devices, sensors, displays, etc.
  • a dry method or a wet method can generally be used.
  • the dry method includes a physical vapor deposition (PVD) or chemical vapor deposition (CVD) method including sputtering, ion plating, and vacuum deposition, and a wet method.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the dry method has the disadvantage of requiring complex equipment and poor adhesion between the substrate and CNTs
  • the wet method has the disadvantage of being relatively simple and economically advantageous, but the CNTs may be damaged by chemical treatment, and the acid Problems with toxicity may arise due to the use of solvents, and there is also a disadvantage in that the adhesion between the substrate and CNT is insufficient.
  • the bonding strength between the substrate and the CNT is insufficient, so a fatal problem occurs in which the CNT film is peeled off during the cleaning process.
  • a patterned CNT film-coated substrate maintains electrical properties without damaging the CNTs, has excellent adhesion to the substrate, and has excellent stability against water or organic solvents because the patterned CNT film is formed at high density and uniformly on the substrate. Research and development is urgently needed.
  • the purpose of the present invention is to provide a patterned CNT film-coated substrate that has excellent stability against organic solvents and high reliability using a click reaction.
  • another object of the present invention is to provide a method for manufacturing a patterned CNT film-coated substrate that is easy to process using a click reaction.
  • the present inventors conducted continuous research to develop a patterned CNT film-coated substrate with excellent adhesion between the CNT film and the substrate and excellent stability to water or organic solvents, and surprisingly, Click When patterning a CNT film using a specific reactive polymer, the CNT film is formed at high density and uniformity, and has excellent stability against water or organic solvents, so it is not easy to peel off even after washing.
  • the present invention was completed by discovering that it could be manufactured through a process.
  • the present invention provides a patterned polymer layer formed from a first polymer on a substrate; and a composite layer formed from a second polymer-CNT composite on the patterned polymer layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer. , providing a patterned CNT film-coated substrate in which the patterned polymer layer and the composite layer are connected through triazole.
  • 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 below.
  • 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 independently integers from 1 to 7;
  • a and b are independently integers of 1 or more.
  • Chemical Formula 4 may be expressed as Chemical Formula 5 below.
  • Ar is a trivalent aromatic radical
  • R 1 and R 2 are each 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 ego;
  • 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
  • z and k are independently integers from 1 to 7;
  • a and b are independently integers of 1 or more.
  • Chemical Formula 5 may be expressed as Chemical Formula 6 below.
  • R 2 and R 3 are each independently C 1-10 alkylene
  • a and b 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 7 below and a repeating unit (m) of Formula 8 below.
  • R 6 and R 7 are independently C 5-50 alkylene
  • R 8 and R 9 are independently C 5-50 alkyl.
  • the CNT film-coated substrate may further include a self-assembled monolayer (SAM) between the substrate and the patterned polymer layer.
  • SAM self-assembled monolayer
  • the self-assembled monolayer may be formed from a compound represented by the following formula (9).
  • 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 includes the steps of (a) coating a first polymer on a substrate and forming a pattern using a mask; (b) contacting the substrate on which the patterned first polymer is formed with a second polymer-CNT composite solution; and (c) forming a patterned polymer layer and a composite layer through a click reaction between the first polymer and the second polymer.
  • step (a) includes (a-1) washing the substrate with a solvent; (a-2) coating a self-assembled monolayer (SAM) on the substrate; (a-3) coating a first polymer on the self-assembled monomolecular layer; (a-4) selectively curing the first polymer using a patterned mask; and (a-5) washing unreacted compounds on the substrate with a solvent.
  • SAM self-assembled monolayer
  • the coating is one selected from the group consisting of spin coating, dip coating, dropping, spray coating, solution casting, bar coating, roll coating, and gravure coating. It can be performed by a method.
  • the second polymer-CNT composite solution may include a second polymer, CNTs, and a solvent.
  • step (c) the density of the CNT film can be adjusted according to the click reaction time.
  • the present invention can provide a CNT-based electronic material including the patterned CNT film-coated substrate described above.
  • the patterned CNT film-coated substrate according to the present invention can have high stability against water or organic solvents because the CNT film is formed uniformly at high density using a click reaction.
  • conventional CNT-based films patterned by CVD (Chemical vapor deposition) or spray coating and spin coating were easily peeled off, resulting in large differences in physical properties between devices and making it difficult to secure reproducibility and reliability.
  • high reproducibility was achieved using a relatively simple method. It has the advantage of being able to easily secure compatibility by manufacturing reliable patterned CNT film coated substrates, and using this, various types of patterns can be produced depending on the industrial field for semiconductors, displays, and electronic devices. Patterned CNT-based electronic materials can be manufactured.
  • Figure 1 is a schematic diagram simply showing a method of manufacturing a patterned CNT film-coated substrate 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.
  • Figure 3 is a graph showing the results of UV-Vis spectroscopy before and after UV curing the acrylate copolymer (i) solution coated in Example 1 and then washing with a solvent.
  • Figure 4 is a photograph of (A) a washed substrate, (B) a substrate coated with acrylate copolymer (i), and (C) a patterned CNT film-coated substrate in Example 1.
  • Figure 5 is an SEM image of the surface of the patterned CNT film-coated substrate of Example 1 measured at 17x, 100x, and 400x.
  • Figure 6 is a graph showing the results of Raman spectroscopy of the coating layer (b') immediately after patterning and before ultrasonic cleaning in Comparative Example 1, and (b') after ultrasonic cleaning.
  • 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 provides a patterned polymer layer formed from a first polymer on a substrate; and a composite layer formed from a second polymer-CNT composite on the patterned polymer layer, wherein the second polymer-CNT composite is CNTs wrapped by a second polymer. , providing a patterned CNT film-coated substrate in which the patterned polymer layer and the composite layer are connected through triazole.
  • 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 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
  • * 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 may be 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 content of 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 patterned 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 is not greatly limited in type as long as it has hydroxy, epoxy, carboxyl, thiol, alkene and alkynyl, specifically alkynyl functional groups in the side chain. You can use it.
  • 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 an alkynyl functional group.
  • 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 the formula 2 may be a copolymer represented by the formula 4 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 Formula 4 may be represented by Formula 5 below.
  • Ar is a trivalent aromatic radical
  • R 1 and R 2 are independently C 1-50 alkylene, C 3-50 cycloalkylene, C 6-50 arylene, C 3-50 heteroaryl.
  • 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 cyclo may be substituted with one or more selected from alkyl, (C 6-30 )ar(C 1-20 )alkyl, C 6-30 aryl and C 3-30 heteroaryl, FG 1 is an alkynyl functional group, z and k may be independently an integer of 1 to 7, and a and b may independently be an integer of 1 or more.
  • R 1 and 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 ) 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: 1 can be satisfied.
  • the first polymer or Formula 5 may be represented by Formula 6 below.
  • R 2 and R 3 are independently C 1-10 alkylene, and a and b are independently an integer of 1 or more. Specifically, R 2 and R 3 may be independently of each other C 1-3 alkylene, and more specifically, R 2 and R 3 may be independently of each other methylene, and a and b may be specifically 0.8 to 2:1. You can be satisfied.
  • z and k in Formula 4 refer to the number of FG 1 included in the p 1 and p 2 repeating units, respectively.
  • z may be 2 and k may be 1.
  • the first polymer or Formula 4 or Formula 5 or Formula 6 may be represented by the following compound, but is not limited thereto.
  • p 1 and p 2 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.
  • the FG 1 functional group may be an alkynyl functional group, and the type of the monomer is not particularly limited as long as it is capable of copolymerization.
  • the type of the monomer is not particularly limited as long as it is a monomer capable of condensation polymerization or addition polymerization.
  • 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 Chemical Formula 4 can be adjusted by adjusting the molar ratio of monomers added to polymerization. That is, the molar ratio of the corresponding monomers added to the polymerization and the ratio of the repeating units p 1 and p 2 may be similar or identical. Specifically, the number of moles of the repeating unit p 1 corresponds to a and the number of moles of p 2 corresponds to b.
  • a:b is 1. : It may be the same or similar to 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 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 a conjugated polymer that is electrically conductive
  • CNTs can be wrapped more effectively, and thus a film with high-density CNTs can be manufactured, and this can be used to create a pattern with excellent electrical properties.
  • CNT film-coated substrates and semiconductor devices can be manufactured.
  • the second polymer or the formula (3) may be a copolymer including a repeating unit (n) of the formula (7) and a repeating unit (m) of the formula (8).
  • R 6 and R 7 are independently C 5-50 alkylene
  • R 8 and R 9 are independently C 5-50 alkyl.
  • R 6 and R 7 may independently be C 5-20 alkylene
  • R 8 and R 9 may independently be C 5-20 alkyl
  • alkylene and alkyl satisfying the above range of carbon numbers may be
  • 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, and each repeating unit is crossed and bonded. It may be an alternating copolymer, and specifically, it may be a random copolymer.
  • n is 0.9 or less, 0.7 or less, preferably 0.5 or less, It may be 0.4 or less, more preferably 0.3 or less, 0.2 or less, or 0.1 or less, and the upper limit is not greatly limited, but may be 0.0001 or more, and is not limited thereto, as long as it does not impair the physical properties targeted by the present invention.
  • 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 patterned CNT film-coated substrate coated with the high-density sc-SWCNT it is possible to exhibit further improved electrical properties.
  • 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 7 and the repeating unit (m) of Formula 8 may be represented by the following Formula 10.
  • R 6 and R 7 may be independently C 5-20 alkylene
  • R 8 , R 9 , R 18 and R 19 may be independently 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 patterned CNT film-coated substrate may further include a self-assembled monolayer (SAM) between the substrate and the patterned polymer layer.
  • 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 may be a self-assembled monolayer formed from a compound represented by the following formula (9).
  • 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.
  • Formula 9 may be represented by Formula 11 below.
  • the compounds represented by Formulas 9 and 11 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. Therefore, the compounds represented by Formulas 9 and 11 and the first polymer can be cross-linked by irradiation with an energy beam.
  • the energy beam include ultraviolet (UV) rays, plasma, etc.
  • the self-assembled monolayer may be formed from the compound represented by Formula 9, 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 layer By fixing the layer, it is possible to manufacture a high-density patterned CNT film-coated substrate that is stable in water and organic solvents and has excellent inter-device reproducibility, which is the goal of the present invention.
  • the patterned CNT film-coated substrate may further include a metal electrode and be manufactured into a semiconductor device.
  • the metal electrode is 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 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 type selected from the group consisting of combinations.
  • the metal electrode may include a source electrode and a drain electrode, and a semiconductor device or 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 can provide a CNT-based electronic material including the patterned CNT film-coated substrate described above.
  • the electronic material can be widely used in various industrial fields such as semiconductors, displays, and sensors depending on the shape of the pattern.
  • the present invention provides a patterned polymer layer formed from a first polymer on a substrate; and a composite layer formed from a second polymer-CNT composite on the patterned polymer layer, wherein the second polymer-CNT composite is CNTs formed by the second polymer.
  • a method for manufacturing a patterned CNT film coated substrate is provided, wherein the patterned polymer layer and the composite layer are connected through triazole.
  • the first polymer may be represented by the formula 2
  • the second polymer may be represented by the formula 3, and compounds containing the first polymer and the second polymer
  • the detailed description is the same as described above and is therefore omitted.
  • the method of manufacturing the patterned CNT film-coated substrate includes the steps of (a) coating a first polymer on a substrate and forming a pattern using a mask; (b) contacting the substrate on which the patterned first polymer is formed with a second polymer-CNT composite solution; and (c) forming a patterned polymer layer and a composite layer through a click reaction between the first polymer and the second polymer.
  • the step (a) may be a step of forming a pattern by coating the first polymer on the substrate and exposing it to light with a mask. Specifically, (a-1) the substrate is coated with a solvent. washing step; (a-2) coating a self-assembled monolayer (SAM) on the substrate; (a-3) coating a first polymer on the self-assembled monomolecular layer; (a-4) selectively curing the first polymer using a patterned mask; and (a-5) washing unreacted compounds on the substrate with a solvent.
  • SAM self-assembled monolayer
  • step (a-1) may be performed to remove impurities on the surface of the substrate, and the solvent may be a commonly used inorganic solvent, organic solvent, or a mixture thereof.
  • 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 coating in step (a-2) 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 monolayer solution may include a compound represented by Formula 9 and a solvent, and the concentration of the compound represented by Formula 9 in the self-assembled monolayer solution may preferably be 0.001 to 3 M, but in particular, Not limited.
  • Formula 9 may be represented by Formula 11, and descriptions of Formulas 9 and 11 are omitted since they 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 9.
  • 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 preferably toluene, but the formula 9 There is no particular limitation as long as the solvent does not react with the compound represented by .
  • the coating is selected from the group consisting of spin coating, dip coating, dropping, spray coating, solution casting, bar coating, roll coating, and gravure coating. It can be performed by one method.
  • a coating solution containing the first polymer and a solvent can be prepared and coated, 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, 1,4-Dioxane, dimethylacetamide (DMA, N,N-dimethylacetamide), dimethylformamide (DMF), tetrahydrofuran (THF), and chloroform.
  • EA ethyl acetate
  • DMA dimethylacetamide
  • DMF dimethylformamide
  • THF tetrahydrofuran
  • 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.
  • step (a-4) is performed by cross-linking the compound represented by Formula 9 and the first polymer by exposure (energy beam irradiation), thereby selectively forming the compound according to the pattern of the mask on the substrate. It may be fixed by curing the first polymer.
  • the curing may be photocuring (UV curing), and the curing time may be from 0.1 to 30 minutes, but is not limited thereto.
  • the curing may be performed using a UV lamp of 365 nm, 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.
  • the CNT film-coated substrate according to the present invention uses a patterned mask to manufacture a substrate on which a patterned first polymer is formed, and then has a uniform CNT density through a process of coating the CNT film through a click reaction and multiple layers. Even after the cleaning process, high-density, stable patterned CNT film-coated substrates can be manufactured, and furthermore, there is an advantage in that various circuit designs are possible depending on the pattern of the mast used.
  • the second polymer-CNT composite solution may include a second polymer, CNTs, and a solvent.
  • the second polymer-CNT composite solution may be a solution in which a second polymer 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.
  • SWCNTs single-walled carbon nanotubes
  • m-SWCNT conductive single-walled carbon nanotubes
  • sc-SWCNT semiconducting single-walled carbon nanotubes
  • 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 second polymer may be a copolymer containing both the repeating unit (n) of Formula 7 and the repeating unit (m) of Formula 8, and the description of the copolymer is described above. Since it is the same as what was described above, it is omitted.
  • step (c) may be performed by reacting the patterned first polymer and the second polymer through a heating or ultrasonic treatment process under a copper catalyst.
  • a patterned polymer layer formed from the first polymer and a composite layer formed from the second polymer-CNT composite can be formed, and the patterned polymer layer and composite layer contain a triazole ring.
  • ultrasonic treatment may be performed at an intensity of 90 to 120 W at a temperature of 50 to 60° C. under a nitrogen atmosphere, and 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 reaction 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 step of washing unreacted compounds with water, organic solvent, etc. may be performed, which may include unreacted compounds such as catalysts, monomers, and polymers used in the reaction. It can be performed to produce a high-purity CNT film by removing .
  • the organic solvent may be any commonly used solvent without particular limitation, and non-limiting examples include one or more solvents selected from methanol, toluene, acetone, 1,4-dioxane, EA, DMA, DMF, THF, and chloroform. You can use it.
  • the cleaning process may be performed through ultrasonic cleaning, and the ultrasonic intensity may be strong at 170 to 230 W.
  • the patterned CNT film-coated substrate according to the present invention is very good because it can maintain a high-density CNT film even after an ultrasonic cleaning process and ensure stability against water and organic solvents.
  • step (d) of forming a source electrode and a drain electrode on the composite layer may be further included, and step (d) is known or commonly used. It can be performed using a method of forming electrodes. 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 the source electrode and drain electrode using a shadow mask can be used. You can.
  • the source electrode and drain electrode may be 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 SnO 2 ), GZO (Ga-doped ZnO), ZTO (zinc tin oxide), GIO (gallium indium oxide),
  • the electrode may be formed of one or more materials selected from the group consisting of ZnO, Pd, Ag, and combinations thereof, and the thickness of the source electrode and drain electrode may be 20 to 100 nm, preferably 20 to 80 nm, but is limited thereto. does not work, and the type and thickness of the electrode can be adjusted depending on the purpose.
  • 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.
  • 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 (iii) 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 (IV) 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 (ii) of Preparation Example 3 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 (ii) 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 dried substrate layer was immersed in the BPS solution of Preparation Example 7 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). At this time, as shown in FIG. 2, it was confirmed whether the self-assembled monolayer (SAM) coating was performed by confirming that the contact angle measurement result for water was 70° or more.
  • a solution of 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. ( Figure 4(B))
  • a patterned shadow mask was placed on the substrate layer coated with acrylate copolymer (i) and exposed to light at an intensity of 727 mJ/cm2 for 1 minute to selectively cure the acrylate copolymer (i). Subsequently, unreacted compounds were removed from the substrate layer by ultrasonic washing in chloroform for 1 hour, the solvent was removed with nitrogen gas, and heat treatment was performed at 120°C for 20 minutes to prepare a substrate on which acrylate copolymer (i) was patterned. ( Figure 4(C))
  • the substrate layer coated and patterned with the acrylate copolymer (i) was placed in a vial, immersed in 1 ml of the second polymer-CNT composite solution of Preparation Example 6, and then 0.003 g of copper sulfate (CuSO 4 ) and sodium ascorbate ( Nitrogen purge was performed by adding 0.019 g of sodium ascorbate 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 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 pattern was printed on the substrate using the second polymer-CNT composite solution of Preparation Example 6 and dried on a hot plate. The above process was repeated twice to coat the patterned film (a') and then sequentially ultrasonic washed for 20 minutes in distilled water, 20 minutes in methanol, 10 minutes in acetone, and 30 minutes in toluene (b') to remove unreacted compounds. After removing the solvent with nitrogen gas, heat treatment was performed at 150°C for 30 minutes to prepare a final patterned CNT coated film substrate.
  • H 2 SO 4 sulfuric acid
  • H 2 O 2 hydrogen peroxide
  • a CNT semiconductor device was manufactured by depositing Au to a thickness of 60 ⁇ m on the CNT coated film substrate of Example 1 and Comparative Example 1 using a shadow mask to form a source electrode and a drain electrode.
  • the electrical characteristic curves (output curve and transfer curve) of the CNT semiconductor device manufactured using the I-V Measurement Software Source Measure Unit (B1500A, Agilent) were measured and shown in FIG. 7.
  • a patterned CNT film-coated substrate was manufactured using a click reaction. Through this, a high-density, highly reliable CNT semiconductor device that is stable in solvents was manufactured. Furthermore, it can be widely used to manufacture electronic materials in various industrial fields such as semiconductors, displays, and electronic devices using various types of pattern masks in a simpler method than before.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Nanotechnology (AREA)

Abstract

L'invention concerne un substrat à motifs revêtu d'un film de CNT, qui peut présenter une grande stabilité vis-à-vis de l'eau ou d'un solvant organique, car un film de CNT est uniformément formé à une densité élevée par utilisation d'une réaction click. En particulier, il est traditionnellement facile d'enlever par pelage un film à motifs à base de CNT obtenus par déposition chimique en phase vapeur (CVD) ou application par pulvérisation ou application à la tournette, de sorte que la différence de propriétés chimiques entre les dispositifs est importante, et il est difficile d'assurer une reproductibilité et une fiabilité, tandis que, dans la présente invention, il est possible de fabriquer un substrat à motifs revêtu d'un film de CNT présentant une grande reproductibilité et une grande fiabilité par un procédé relativement simple et, grâce à l'utilisation de ce dernier, il est possible de former différents types de motifs convenant aux domaines industriels des semiconducteurs, des affichages et des dispositifs électroniques.
PCT/KR2023/004257 2022-03-30 2023-03-30 Substrat à motifs, revêtu d'un film de cnt, utilisant une réaction click et procédé de fabrication associé WO2023191535A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2022-0039532 2022-03-30
KR1020220039532A KR102488388B1 (ko) 2022-03-30 2022-03-30 클릭반응을 이용한 패턴화된 cnt 필름 코팅 기판 및 이의 제조방법

Publications (1)

Publication Number Publication Date
WO2023191535A1 true WO2023191535A1 (fr) 2023-10-05

Family

ID=84900041

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/004257 WO2023191535A1 (fr) 2022-03-30 2023-03-30 Substrat à motifs, revêtu d'un film de cnt, utilisant une réaction click et procédé de fabrication associé

Country Status (2)

Country Link
KR (1) KR102488388B1 (fr)
WO (1) WO2023191535A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102488388B1 (ko) * 2022-03-30 2023-01-13 한국화학연구원 클릭반응을 이용한 패턴화된 cnt 필름 코팅 기판 및 이의 제조방법

Citations (5)

* 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
KR101358941B1 (ko) * 2007-05-07 2014-02-27 한국과학기술원 이온성 액체를 이용한 전도성 탄소나노튜브 및 이를 이용한바이오센서
KR20140033555A (ko) * 2012-08-29 2014-03-19 삼성전자주식회사 탄소나노튜브 분리 방법
KR101937608B1 (ko) * 2018-03-02 2019-01-11 권형준 탄소나노튜브 기반 유연 투명 전도성 필름의 제조방법.
KR102488388B1 (ko) * 2022-03-30 2023-01-13 한국화학연구원 클릭반응을 이용한 패턴화된 cnt 필름 코팅 기판 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101358941B1 (ko) * 2007-05-07 2014-02-27 한국과학기술원 이온성 액체를 이용한 전도성 탄소나노튜브 및 이를 이용한바이오센서
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
KR101937608B1 (ko) * 2018-03-02 2019-01-11 권형준 탄소나노튜브 기반 유연 투명 전도성 필름의 제조방법.
KR102488388B1 (ko) * 2022-03-30 2023-01-13 한국화학연구원 클릭반응을 이용한 패턴화된 cnt 필름 코팅 기판 및 이의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FONG DARRYL, ANDREWS GRACE M., ADRONOV ALEX: "Functionalization of polyfluorene-wrapped carbon nanotubes via copper-mediated azide–alkyne cycloaddition", POLYMER CHEMISTRY, ROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE, vol. 9, no. 21, 1 January 2018 (2018-01-01), Cambridge , pages 2873 - 2879, XP093096142, ISSN: 1759-9954, DOI: 10.1039/C8PY00377G *

Also Published As

Publication number Publication date
KR102488388B1 (ko) 2023-01-13

Similar Documents

Publication Publication Date Title
WO2016053014A1 (fr) Procédé de fabrication d'un substrat à motifs
WO2016053007A1 (fr) Procédé de fabrication d'un substrat à motifs
WO2015084122A1 (fr) Copolymère bloc
WO2015084124A1 (fr) Copolymère bloc
WO2018097665A2 (fr) Composition et dispositif électroluminescent organique
WO2015084121A1 (fr) Copolymère bloc
WO2015084120A1 (fr) Monomère et copolymère bloc
WO2015084125A1 (fr) Copolymère bloc
WO2015084123A1 (fr) Copolymère bloc
WO2015108386A1 (fr) Nouveau composé de β-ester d'oxime fluorène, amorceur de photopolymérisation comprenant ce composé et composition de résine photosensible
WO2013100409A1 (fr) Monomère pour une composition de masque dur, composition de masque dur comprenant le monomère, et procédé permettant de former un motif à l'aide de la composition de masque dur
WO2020076122A1 (fr) Composé, composition de résine photosensible le comprenant, motif de résine photosensible le comprenant, et procédé de fabrication d'un motif de résine photosensible
WO2023191535A1 (fr) Substrat à motifs, revêtu d'un film de cnt, utilisant une réaction click et procédé de fabrication associé
WO2020111522A1 (fr) Composition de résine photosensible, film et dispositif électronique
WO2015190762A2 (fr) Dérivé à cycles fusionnés et cellule solaire organique le comprenant
WO2019066305A1 (fr) Copolymère et cellule solaire organique le comprenant
WO2023177186A1 (fr) Film de cnt utilisant une réaction click, biocapteur à base de cnt l'utilisant, et son procédé de fabrication
WO2019004605A1 (fr) Cellule solaire organique
WO2019225989A1 (fr) Composé, composition de revêtement le comprenant, et diode électroluminescente organique
WO2014133285A1 (fr) Film mince conducteur, son procédé de production et élément électronique le contenant
WO2014104496A1 (fr) Monomère, composition de masque dur comprenant le monomère et procédé de formation de motif par utilisation de la composition de masque dur
WO2021040328A1 (fr) Dispositif électroluminescent organique
WO2019083235A1 (fr) Composé hétérocyclique et dispositif électronique organique le comprenant
WO2021132865A1 (fr) Composé de résine polymère, son procédé de production, et composition de résine photosensible le comprenant
WO2019146978A1 (fr) Polymère, composition de revêtement le comprenant, et dispositif électroluminescent organique l'utilisant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23781387

Country of ref document: EP

Kind code of ref document: A1