CN112652424A - Preparation method of carbon nano tube composite transparent conductive film - Google Patents
Preparation method of carbon nano tube composite transparent conductive film Download PDFInfo
- Publication number
- CN112652424A CN112652424A CN202110185853.7A CN202110185853A CN112652424A CN 112652424 A CN112652424 A CN 112652424A CN 202110185853 A CN202110185853 A CN 202110185853A CN 112652424 A CN112652424 A CN 112652424A
- Authority
- CN
- China
- Prior art keywords
- film
- nano tube
- carbon nano
- mxene
- copper
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 65
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 230000008021 deposition Effects 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- -1 polyoxypropylene Polymers 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 238000002791 soaking Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 12
- 229920002799 BoPET Polymers 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 206010070834 Sensitisation Diseases 0.000 claims description 9
- 230000008313 sensitization Effects 0.000 claims description 9
- 239000002238 carbon nanotube film Substances 0.000 claims description 6
- 239000013504 Triton X-100 Substances 0.000 claims description 5
- 229920004890 Triton X-100 Polymers 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 5
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 5
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical group [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 5
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 239000010949 copper Substances 0.000 abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052802 copper Inorganic materials 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 10
- 239000010408 film Substances 0.000 description 89
- 239000000243 solution Substances 0.000 description 33
- 238000000151 deposition Methods 0.000 description 22
- 238000002834 transmittance Methods 0.000 description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The invention discloses a preparation method of a carbon nano tube composite transparent conductive film, which comprises the following steps: (1) preparing a PET substrate; (2) preparing carbon nano tube-MXene ink; (3) preparing an electroless deposition solution: mixing Cu2+Mixing copper salt with concentration of 0.05-0.3 mol/L, reducing agent with concentration of 10-30 g/L, ammonium chloride with concentration of 3-8 g/L, thiourea with concentration of 0.01-0.06 g/L, trihydroxy polyoxypropylene ether with concentration of 0.5-5 g/L and residual water; (4) electroless deposition of metallic copper on the surface of the carbon nanotube-MXene; (5) followed by Ag particles growing on MXene residual sites. The preparation method has simple steps and easily realized reaction conditions.
Description
Technical Field
The invention relates to the field of transparent conductive films, in particular to a preparation method of a carbon nano tube composite transparent conductive film.
Background
Indium Tin Oxide (ITO) is currently the most widely used transparent electrode material, and is used in the fields of display screens, touch screens, transparent electrodes, and the like. However, as electronic devices are developed to be light, small and flexible, conventional ITO has poor flexibility and is too expensive to meet people's needs. Therefore, development of transparent conductive thin film materials with excellent photoelectric properties and bending resistance has been the focus of attention of research and development personnel. In the materials, particularly, one-dimensional nano materials such as carbon nanotubes and metal nanowires, and two-dimensional nano materials such as graphene and MXene are mainly used, so that the materials have excellent conductivity, visible light transmittance and flexibility, and have become powerful competitors of the traditional ITO materials. However, in the prior art, although there are cases of preparing a transparent conductive film by compounding one-dimensional and two-dimensional nano materials and cases of preparing a transparent conductive film by chemically plating gold on a nano material to improve the conductivity thereof, the conductivity and the light transmittance of the film are still limited, and thus a film material having both excellent conductivity and light transmittance is urgently needed to meet the application.
Disclosure of Invention
The present invention aims to provide a carbon nanotube composite transparent conductive film and a preparation method thereof, so as to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a carbon nano tube composite transparent conductive film comprises the following steps:
(1) preparing a PET substrate: firstly, soaking and washing a PET film by using deionized water, acetone and ethanol respectively, wherein the soaking time is 5-15 min, and after drying the cleaned PET film, carrying out ultraviolet ozone treatment for 10-30 min for coating;
since the surface of PET is provided with more greasy substances and dust, which have great influence on the light transmittance of PET, the cleaning and the ultraviolet ozone treatment are both used for obtaining a PET film with a clean surface.
(2) Preparing carbon nano tube-MXene ink: mixing 0.2-0.8 wt% of carbon nano tube, 0.1-0.4 wt% of MXene, 0.01-0.1 wt% of dispersant, 0.005-0.05 wt% of flatting agent, 0.03-0.1wt% of surfactant and the rest of water, and uniformly stirring for later use;
the conductivity of the composite material obtained by the carbon nano tube and the MXene at the preferable mass ratio is better than that of any single material, because the addition of the MXene can reduce the junction resistance at the junction of the carbon nano tube and shows a synergistic effect on the conductivity. The effect of the dispersing agent in the ink is to obtain uniformly dispersed conductive ink, the effect of the leveling agent is to flatten and uniform the ink when being dried to form a film, and the effect of the surfactant is to reduce the surface tension of the aqueous solution, so that the ink can wet the surface of the PET, and holes are prevented from being formed during drying.
(3) Preparing an electroless deposition solution: mixing Cu2+Copper salt with concentration of 0.05-0.3 mol/L, reducing agent of 10-30 g/L, 3-8 g/L of ammonium chloride, 0.01-0.06 g/L of thiourea, 0.5-5 g/L of trihydroxy polyoxypropylene ether and the rest of water are mixed, stirred uniformly, and the temperature is raised to 75-90 ℃ for later use;
wherein the ammonium chloride has the function of adjusting the pH value of the electroless deposition solution due to self-presented weak acidity, the thiourea has the function of inhibiting side reactions generated during electroless gold plating so as to ensure that the main reaction is stably carried out, and the trihydroxy polyoxypropylene ether with the optimized concentration has the functions of improving the activity of the electroless deposition solution and catalyzing the reaction to be carried out.
(4) Preparing a copper-plated carbon nano tube-MXene film: uniformly coating the carbon nano tube-MXene ink on a PET substrate treated by ultraviolet ozone, and drying at the temperature of 60-80 ℃ for 5-15 min; then soaking the dried carbon nanotube film in a tin dichloride solution for sensitization for 1-5 min and a palladium ion solution for activation for 5-10 min in sequence; finally, soaking the activated carbon nanotube film in electroless deposition solution for reaction for 30-50 min, continuously stirring in the reaction process to ensure that the reaction solution is fully contacted with the film, and after the reaction is finished, washing the film clean and drying to obtain the copper-plated carbon nanotube-MXene film;
the sensitization and activation are characterized in that a layer of reductive tin dichloride is formed on the surfaces of the carbon nano tubes and MXene, palladium ions are reduced and deposited on the surfaces of the carbon nano tubes and the MXene, and therefore palladium atom activation centers are formed and Cu is assisted2+Deposited on the surface thereof. The resistance of the junction of the carbon nano tube and MXene after copper plating is effectively reduced, so that the conductivity is improved.
(5) Preparing a carbon nano tube composite transparent conductive film: soaking the copper-plated carbon nano tube-MXene film in 1-10 mg/mL AgNO3And (3) putting the carbon nano tube in the solution for 3-10 min to finally prepare the carbon nano tube composite transparent conductive film.
MXene has similar reducing property of active metal and is mixed with AgNO3The solution mixing can grow Ag particles with the particle size of about 20-50 nm on the residual sites, and the size of the particle size is far smaller than the wavelength of visible light, so that the high permeability of the carbon nano tube composite transparent conductive film to the visible light is ensured. The copper-plated carbon nano tube-MXene can also replaceAnd a layer of silver with better conductivity further improves the conductivity of the film.
Preferably, the dispersing agent is one or more of hydroxymethyl cellulose, polyvinyl alcohol, polyurethane and polyacrylic acid; the leveling agent is one or more of aqueous leveling agents BYK-306, BYK-333, BYK-377, BYK-394 and BYK-UV 3505; the surfactant is Triton X-100 or fluorocarbon surfactant.
Preferably, the copper salt can be one or more of copper sulfate, copper chloride and copper nitrate.
Preferably, the pH of the electroless deposition solution is between 4.5 and 6. In this pH range, the electroless deposition reaction can be allowed to proceed gently while Cu (OH) is prevented2And (4) generating.
Preferably, the palladium ion salt can be one or more of sodium tetrachloropalladate, dichlorodiammine palladium, palladium nitrate and palladium chloride.
Preferably, the concentration of the tin dichloride is 10-20 g/L, and the concentration of the palladium ion salt is 0.1-0.5 g/L.
Preferably, the coating mode can be one of bar coating, spin coating or spray coating, and is preferably bar coating. The uniformity of the film produced by bar coating is higher due to the fine and uniform thread of the bar.
Preferably, the diameter of the carbon nanotube is 20-60 nm, and the aspect ratio is 800-1200; the MXene has 1-5 layers and a transverse dimension of 0.5-3 μm. The carbon nano tube with smaller diameter can improve the light transmission of the film, and the high length-diameter ratio can obtain more nodes during film forming, so that the conductivity of the film is improved; as the number of MXene layers is smaller, the conductivity is higher, and it is preferable to use 1 to 5 MXene layers.
Preferably, the stirring speed is 300-1500 r/min.
The invention also provides the carbon nano tube composite transparent conductive film prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the junction resistance can be greatly reduced and the conductivity of the film can be improved by electroless deposition of metal Cu on the basis of the carbon nano tube-MXene film. The method is different from the prior art that a layer of metal is plated on the nano material first and then the film is prepared. The difference lies in that the carbon nanotube junctions in the finally prepared films are different, the structure of the junctions is that two carbon nanotubes with core-shell structures are mutually overlapped, and the carbon nanotubes are not directly contacted, so that the contact area is limited, and the conductivity is worse; the structure of the former junction is that the overlapping position of two carbon nano tubes is the center, the deposited metal copper is coated around the overlapping position, the contact area is increased, and the conductivity is better.
(2) Because the light transmission of copper is poor, the diameter of the copper-plated carbon nano tube can be controlled within 100 nm by controlling the time of electroless deposition within 30-50 min, so that the conductivity of the film can be improved, and the light transmission of the film can not be reduced.
(3) The invention utilizes the reducibility of MXene and residual sites after copper plating to deposit Ag particles, preferably AgNO3The concentration is 1-10 mg/mL, and the particle size of Ag particles can be controlled between 20-50 nm within 3-10 min of reaction time; and meanwhile, MXene and copper can be protected by replacing a silver layer with lower activity than copper on the surface of the copper coating. The method improves the conductivity and the oxidation resistance of the carbon nano tube composite transparent conductive film and ensures the light transmission of the carbon nano tube composite transparent conductive film.
(4) The carbon nano tube, MXene and other materials used in the method are easily available materials in the market, and compared with an electrochemical deposition preparation method, the electroless deposition method used in the method is simple in preparation process and saves energy.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The invention provides a preparation method of a carbon nano tube composite transparent conductive film, which comprises the following steps:
(1) preparing a PET substrate: firstly, soaking and washing a PET film by using deionized water, acetone and ethanol respectively, wherein the soaking time is 5 min, and after drying the cleaned PET film, carrying out ultraviolet ozone treatment for 10 min for coating;
(2) preparing carbon nano tube-MXene ink: mixing 0.2 wt% of carbon nano tube, 0.1wt% of MXene, 0.01 wt% of dispersant, 0.005 wt% of flatting agent, 0.03wt% of surfactant and the rest of water, and uniformly stirring for later use;
(3) preparing an electroless deposition solution: mixing Cu2+Mixing copper salt with the concentration of 0.05 mol/L, reducing agent with the concentration of 10 g/L, ammonium chloride with the concentration of 3 g/L, thiourea with the concentration of 0.01 g/L, trihydroxy polyoxypropylene ether with the concentration of 0.5 g/L and the rest water, stirring uniformly, raising the temperature to 75 ℃, and preserving the temperature for later use;
(4) preparing a copper-plated carbon nano tube-MXene film: uniformly coating the carbon nano tube-MXene ink on a PET substrate treated by ultraviolet ozone, and drying at 60 ℃ for 5 min; then, the dried carbon nanotube film is sequentially soaked in tin dichloride solution for sensitization for 1 min and palladium ion solution for activation for 5 min; finally, soaking the activated carbon nanotube film in electroless deposition solution for reaction for 30 min, continuously stirring in the reaction process to ensure that the reaction solution is fully contacted with the film, and after the reaction is finished, washing the film clean and drying to obtain the copper-plated carbon nanotube-MXene film;
(5) preparing a carbon nano tube composite transparent conductive film: soaking the copper-plated carbon nano tube-MXene film in 1 mg/mL AgNO3And (5) standing in the solution for 10 min to finally prepare the carbon nano tube composite transparent conductive film.
Wherein MXene is Ti3C2Tx(ii) a The dispersing agent is hydroxymethyl cellulose, the leveling agent is a water-based leveling agent BYK-306, and the surfactant is triton X-100; the copper salt is copper sulfate; the pH value of the electroless deposition solution is 4.5; the palladium ion salt is sodium tetrachloropalladate; the concentration of the tin dichloride is 10 g/L, and the concentration of the palladium ion salt is 0.1 g/L; the coating mode is bar coating; the diameter of the carbon nano tube is 20 nm, and the length-diameter ratioIs 800; the MXene has 1 layer and 0.5 μm transverse dimension; the stirring speed is 300 r/min.
The invention also provides the carbon nano tube composite transparent conductive film prepared by the method.
Example two
The invention provides a preparation method of a carbon nano tube composite transparent conductive film, which comprises the following steps:
(1) preparing a PET substrate: firstly, soaking and washing a PET film by using deionized water, acetone and ethanol respectively, wherein the soaking time is 15 min, and after drying the cleaned PET film, carrying out ultraviolet ozone treatment for 30 min for coating;
(2) preparing carbon nano tube-MXene ink: mixing 0.8 wt% of carbon nano tube, 0.4 wt% of MXene, 0.1wt% of dispersant, 0.05 wt% of flatting agent, 0.1wt% of surfactant and the rest of water, and uniformly stirring for later use;
(3) preparing an electroless deposition solution: mixing Cu2+Mixing copper salt with the concentration of 0.3 mol/L, reducing agent with the concentration of 30 g/L, ammonium chloride with the concentration of 8 g/L, thiourea with the concentration of 0.06 g/L, trihydroxy polyoxypropylene ether with the concentration of 5 g/L and the rest water, stirring uniformly, raising the temperature to 90 ℃, and preserving the temperature for later use;
(4) preparing a copper-plated carbon nano tube-MXene film: uniformly coating the carbon nano tube-MXene ink on a PET substrate treated by ultraviolet ozone, and drying for 15 min at the temperature of 80 ℃; then, the dried carbon nanotube film is sequentially soaked in a tin dichloride solution for sensitization for 5 min and a palladium ion solution for activation for 10 min; finally, soaking the activated carbon nanotube film in electroless deposition solution for reaction for 50 min, continuously stirring in the reaction process to ensure that the reaction solution is fully contacted with the film, and after the reaction is finished, washing the film clean and drying to obtain the copper-plated carbon nanotube-MXene film;
(5) preparing a carbon nano tube composite transparent conductive film: soaking the copper-plated carbon nano tube-MXene film in AgNO of 10 mg/mL3And (3) putting the carbon nano tube in the solution for 3 min to finally prepare the carbon nano tube composite transparent conductive film.
Wherein MXene is Ti3C2Tx(ii) a The dispersing agent is hydroxymethyl cellulose, the leveling agent is a water-based leveling agent BYK-306, and the surfactant is triton X-100; the copper salt is copper sulfate; the pH value of the electroless deposition solution is 6; the palladium ion salt is sodium tetrachloropalladate; the concentration of the tin dichloride is 20 g/L, and the concentration of the palladium ion salt is 0.5 g/L; the coating mode is bar coating; the diameter of the carbon nano tube is 60 nm, and the length-diameter ratio is 1200; the MXene has 5 layers and 3 μm transverse dimension; the stirring speed is 1500 r/min.
The invention also provides the carbon nano tube composite transparent conductive film prepared by the method.
EXAMPLE III
The invention provides a preparation method of a carbon nano tube composite transparent conductive film, which comprises the following steps:
(1) preparing a PET substrate: firstly, soaking and washing a PET film by using deionized water, acetone and ethanol respectively, wherein the soaking time is 10 min, and after drying the cleaned PET film, carrying out ultraviolet ozone treatment for 20 min for coating;
(2) preparing carbon nano tube-MXene ink: mixing 0.4 wt% of carbon nano tube, 0.2 wt% of MXene, 0.05 wt% of dispersant, 0.01 wt% of flatting agent, 0.08wt% of surfactant and the rest of water, and uniformly stirring for later use;
(3) preparing an electroless deposition solution: mixing Cu2+Mixing copper salt with the concentration of 0.1 mol/L, 15 g/L reducing agent, 5 g/L ammonium chloride, 0.03 g/L thiourea, 2 g/L trihydroxy polyoxypropylene ether and the rest water, stirring uniformly, raising the temperature to 85 ℃, and preserving the heat for later use;
(4) preparing a copper-plated carbon nano tube-MXene film: uniformly coating the carbon nano tube-MXene ink on a PET substrate treated by ultraviolet ozone, and drying at 70 ℃ for 10 min; then, the dried carbon nanotube film is sequentially soaked in tin dichloride solution for sensitization for 3 min and palladium ion solution for activation for 8 min; finally, soaking the activated carbon nanotube film in electroless deposition solution for reaction for 45 min, continuously stirring in the reaction process to ensure that the reaction solution is fully contacted with the film, and after the reaction is finished, washing the film clean and drying to obtain the copper-plated carbon nanotube-MXene film;
(5) preparing a carbon nano tube composite transparent conductive film: soaking the copper-plated carbon nano tube-MXene film in AgNO of 3 mg/mL3And (5) dissolving in the solution for 5 min to finally prepare the carbon nano tube composite transparent conductive film.
Wherein MXene is Ti3C2Tx(ii) a The dispersing agent is hydroxymethyl cellulose, the leveling agent is a water-based leveling agent BYK-306, and the surfactant is triton X-100; the copper salt is copper sulfate; the pH value of the electroless deposition solution is 5; the palladium ion salt is sodium tetrachloropalladate; the concentration of the tin dichloride is 16 g/L, and the concentration of the palladium ion salt is 0.2 g/L; the coating mode is bar coating; the diameter of the carbon nano tube is 30 nm, and the length-diameter ratio is 1000; the MXene has 2 layers and 2 μm transverse dimension; the stirring speed is 800 r/min.
The invention also provides the carbon nano tube composite transparent conductive film prepared by the method.
In order to test the performance of each film, the sheet resistance, the light transmittance and the haze of the film are respectively tested. Wherein the square resistor is obtained by cutting the thin film into 10 × 10 cm2After the specification is obtained, a four-probe method is used for testing 25 points at equal intervals and an average value is taken to obtain the product, wherein the smaller the square resistance is, the better the conductivity of the film is; the light transmittance and the haze of the film are detected by an ultraviolet-visible spectrophotometry and respectively represent the transmittance and the scattering rate of the film to light, and the higher the light transmittance and the lower the haze represent the better the optical performance of the film.
Through comparative experiments on the three groups of examples, the carbon nanotube composite transparent conductive film with excellent performance can be prepared by each group of examples. Wherein the sheet resistance of the carbon nanotube composite transparent conductive film prepared in the first embodiment is 112 Ω/□, the light transmittance is 90.1%, and the haze is 2.3%; wherein the sheet resistance of the carbon nanotube composite transparent conductive film prepared in the second embodiment is 128 Ω/□, the light transmittance is 90.9%, and the haze is 1.8%; the sheet resistance of the carbon nanotube composite transparent conductive film prepared in the third embodiment is 125 Ω/□, the light transmittance is 90.3%, and the haze is 2.0%.
Comparative example 1: the difference from the third embodiment is that the carbon nanotube-MXene ink is plated with copper by electroless deposition, and then the carbon nanotube-MXene ink is coated with the ink to prepare the film, wherein the square resistance of the carbon nanotube composite transparent conductive film is 217 omega/□, the light transmittance is 90.5%, and the haze is 2.4%. It can be seen that the sheet resistance of the film prepared by plating copper on the nano material is greatly increased under the condition of similar light transmittance, which is caused by the reduction of the junction contact area.
Comparative example 2: the difference from the third embodiment is that copper is plated on the carbon nanotube film by electroless deposition, and then a layer of MXene is coated, so that the square resistance of the prepared carbon nanotube composite transparent conductive film is 147 Ω/□, the light transmittance is 90.8%, and the haze is 1.9%. It can be seen that the light transmittance of the film slightly increases because MXene does not participate in the copper plating, but also the sheet resistance of the film increases because the junction resistance decreases because the contact area of MXene with the copper-plated carbon nanotubes decreases.
Comparative example 3: the difference from the third example is that the reaction time of electroless deposition is 2 hours, instead of compounding with phenolic resin through polymerization, the square resistance of the prepared carbon nanotube composite transparent conductive film is 86 Ω/□, the light transmittance is 86.1%, and the haze is 3.5%. The diameter of the carbon nanotube is continuously increased due to the excessive deposition of the metal copper, and although the conductivity of the thin film is improved, the light transmittance of the whole thin film is greatly reduced.
Comparative example 4: the difference from the third embodiment is that MXene reduces AgNO3The reaction time is 30 min, the square resistance of the prepared carbon nano tube composite transparent conductive film is 98 omega/□, the light transmittance is 88.4%, and the haze is 4.7%. Due to MXene and AgNO3The reaction time is prolonged, so that most MXene is reduced, the particle size of Ag particles is too large, the light scattering effect is also increased, and the haze of the film is greatly improved.
Comparative example 5: the difference from the third embodiment is that copper is directly plated without sensitizing and activating the carbon nano tube-MXene film, and the square resistance of the prepared carbon nano tube composite transparent conductive film is 148 omega-□, light transmittance 91.0% and haze 1.8%. Cu due to no sensitization and activation treatment to the carbon nano tube-MXene film2+Is directly reduced in the solution and forms a precipitate, so that the optical performance and the electric conductivity of the film are not effectively improved, which is equivalent to no copper plating.
Comparative example 6: the difference from the third example is that the sensitization time of the tin dichloride and the activation time of the palladium ions are both 30 min, the square resistance of the prepared carbon nanotube composite transparent conductive film is 156 Ω/□, the light transmittance is 88.2%, and the haze is 3.7%. The increase of sensitization and activation time causes excessive black palladium to be deposited on the surface of the carbon nano tube, which not only reduces the optical performance of the film, but also hinders copper plating and Ag particle growth at the later stage, and increases the square resistance of the film.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1. A preparation method of a carbon nano tube composite transparent conductive film is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a PET substrate: firstly, soaking and washing a PET film by using deionized water, acetone and ethanol respectively, wherein the soaking time is 10 min, and after drying the cleaned PET film, carrying out ultraviolet ozone treatment for 20 min for coating;
(2) preparing carbon nano tube-MXene ink: mixing 0.4 wt% of carbon nano tube, 0.2 wt% of MXene, 0.05 wt% of dispersant, 0.01 wt% of flatting agent, 0.08wt% of surfactant and the rest of water, and uniformly stirring for later use;
(3) preparing an electroless deposition solution: mixing Cu2+Copper salt with the concentration of 0.1 mol/L, 15 g/L reducing agent, 5 g/L ammonium chloride, 0.03 g/L thiourea, 2 g/L trihydroxy polyoxypropylene ether and the rest water are mixed and stirred evenly, the temperature is raised to 85 ℃, and then the temperature is keptStandby;
(4) preparing a copper-plated carbon nano tube-MXene film: uniformly coating the carbon nano tube-MXene ink on a PET substrate treated by ultraviolet ozone, and drying at 70 ℃ for 10 min; then, the dried carbon nanotube film is sequentially soaked in tin dichloride solution for sensitization for 3 min and palladium ion solution for activation for 8 min; finally, soaking the activated carbon nanotube film in electroless deposition solution for reaction for 45 min, continuously stirring in the reaction process to ensure that the reaction solution is fully contacted with the film, and after the reaction is finished, washing the film clean and drying to obtain the copper-plated carbon nanotube-MXene film;
(5) preparing a carbon nano tube composite transparent conductive film: soaking the copper-plated carbon nano tube-MXene film in AgNO of 3 mg/mL3And (5) dissolving in the solution for 5 min to finally prepare the carbon nano tube composite transparent conductive film.
Wherein MXene is Ti3C2Tx(ii) a The dispersing agent is hydroxymethyl cellulose, the leveling agent is a water-based leveling agent BYK-306, and the surfactant is triton X-100; the copper salt is copper sulfate; the pH value of the electroless deposition solution is 5; the palladium ion salt is sodium tetrachloropalladate; the concentration of the tin dichloride is 16 g/L, and the concentration of the palladium ion salt is 0.2 g/L; the coating mode is bar coating; the diameter of the carbon nano tube is 30 nm, and the length-diameter ratio is 1000; the MXene has 2 layers and 2 μm transverse dimension; the stirring speed is 800 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110185853.7A CN112652424A (en) | 2020-07-27 | 2020-07-27 | Preparation method of carbon nano tube composite transparent conductive film |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010732086.2A CN111933351B (en) | 2020-07-27 | 2020-07-27 | Carbon nano tube composite transparent conductive film and preparation method thereof |
| CN202110185853.7A CN112652424A (en) | 2020-07-27 | 2020-07-27 | Preparation method of carbon nano tube composite transparent conductive film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010732086.2A Division CN111933351B (en) | 2020-07-27 | 2020-07-27 | Carbon nano tube composite transparent conductive film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112652424A true CN112652424A (en) | 2021-04-13 |
Family
ID=73314226
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110185860.7A Pending CN112652425A (en) | 2020-07-27 | 2020-07-27 | Preparation method of carbon nano tube composite transparent conductive film |
| CN202110185853.7A Pending CN112652424A (en) | 2020-07-27 | 2020-07-27 | Preparation method of carbon nano tube composite transparent conductive film |
| CN202010732086.2A Active CN111933351B (en) | 2020-07-27 | 2020-07-27 | Carbon nano tube composite transparent conductive film and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110185860.7A Pending CN112652425A (en) | 2020-07-27 | 2020-07-27 | Preparation method of carbon nano tube composite transparent conductive film |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010732086.2A Active CN111933351B (en) | 2020-07-27 | 2020-07-27 | Carbon nano tube composite transparent conductive film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN112652425A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114324514A (en) * | 2021-11-30 | 2022-04-12 | 南通大学 | PET-based flexible electrode and preparation method and application thereof |
| CN114883050A (en) * | 2022-04-26 | 2022-08-09 | 苏州博濬新材料科技有限公司 | Low-temperature sintering copper paste based on multi-conductive network structure filler and preparation method thereof |
| CN118639434A (en) * | 2024-08-14 | 2024-09-13 | 淮安金利达包装有限公司 | High-strength composite fiber material and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112924506B (en) * | 2021-03-08 | 2023-01-10 | 湖南科技大学 | Preparation method of simple electrochemical micro sensor, product and application thereof |
| CN113418975A (en) * | 2021-07-08 | 2021-09-21 | 江苏大学 | Novel metal ion stripping voltammetry detection method free of electrodeposition technology |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031349A1 (en) * | 2007-09-07 | 2009-03-12 | Nec Corporation | Semiconductor device using carbon nanotube film and process for producing the semiconductor device |
| CN102528038A (en) * | 2011-12-31 | 2012-07-04 | 浙江工业大学 | Preparation method of copper/carbon nanotube composite superhydrophobic material |
| CN103531304A (en) * | 2013-09-18 | 2014-01-22 | 天津工业大学 | Method for quickly preparing large-area carbon nanometer tube flexible transparent conductive thin films and improving electric conductibility of thin films |
| CN104934108A (en) * | 2014-12-31 | 2015-09-23 | 重庆元石石墨烯技术开发有限责任公司 | Metallic nanowire-graphene bridge structural composite material and preparation method thereof |
| CN109827945A (en) * | 2019-02-28 | 2019-05-31 | 合肥工业大学 | A kind of preparation method of high SERS activity Ag/MXene-Ti3C2 composite material |
| CN111132533A (en) * | 2019-12-31 | 2020-05-08 | 浙江工业大学 | MXene/silver nanowire composite electromagnetic shielding film |
| CN111180701A (en) * | 2020-01-06 | 2020-05-19 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111223587A (en) * | 2020-01-16 | 2020-06-02 | 南开大学 | Dendritic layered self-assembled flexible conductive film and preparation method thereof |
| CN111341497A (en) * | 2020-03-13 | 2020-06-26 | 浙江大学 | Preparation method of silver nanowire-MXene composite transparent conductive film |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012059417A (en) * | 2010-09-06 | 2012-03-22 | Fujifilm Corp | Transparent conductive film, method of manufacturing the same, electronic device, and organic thin film solar cell |
| CN103422079B (en) * | 2012-05-22 | 2016-04-13 | 比亚迪股份有限公司 | A kind of chemical bronze plating liquid and preparation method thereof |
| CN103903817B (en) * | 2014-03-18 | 2016-04-13 | 中科院广州化学有限公司南雄材料生产基地 | A kind of preparation method of transparent conductive film and application thereof |
| JP2016018713A (en) * | 2014-07-09 | 2016-02-01 | 株式会社クラレ | Conductive film |
| CN104498916B (en) * | 2014-11-24 | 2017-04-26 | 广西大学 | Method used for preparing aluminium-doped zinc oxide thin film via electroless deposition |
| CN105788754B (en) * | 2014-12-24 | 2018-07-06 | 深圳市润麒麟科技发展有限公司 | Carbon nano tube transparent conductive thin-film and preparation method thereof |
| CN106270500B (en) * | 2016-09-30 | 2019-02-19 | 昆明理工大学 | A kind of carbon nano tube surface uniformly coats the method and device of metallic silver |
| CN106910551B (en) * | 2017-02-14 | 2019-01-08 | 哈尔滨工业大学深圳研究生院 | A kind of plating metal enhancing transparent conductive film and preparation method thereof |
| CN109338134A (en) * | 2018-09-08 | 2019-02-15 | 天津大学 | A kind of preparation method of nickel-plating carbon nanotube reinforced aluminum matrix composites |
| CN109261155B (en) * | 2018-09-25 | 2021-05-07 | 中南大学 | Carbon nanotube/copper-zinc alloy composite material and preparation method and application thereof |
| CN110316719A (en) * | 2019-06-24 | 2019-10-11 | 武汉工程大学 | A kind of MXene/ nitrogen-doped carbon nanometer pipe laminated film and preparation method thereof |
-
2020
- 2020-07-27 CN CN202110185860.7A patent/CN112652425A/en active Pending
- 2020-07-27 CN CN202110185853.7A patent/CN112652424A/en active Pending
- 2020-07-27 CN CN202010732086.2A patent/CN111933351B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031349A1 (en) * | 2007-09-07 | 2009-03-12 | Nec Corporation | Semiconductor device using carbon nanotube film and process for producing the semiconductor device |
| CN102528038A (en) * | 2011-12-31 | 2012-07-04 | 浙江工业大学 | Preparation method of copper/carbon nanotube composite superhydrophobic material |
| CN103531304A (en) * | 2013-09-18 | 2014-01-22 | 天津工业大学 | Method for quickly preparing large-area carbon nanometer tube flexible transparent conductive thin films and improving electric conductibility of thin films |
| CN104934108A (en) * | 2014-12-31 | 2015-09-23 | 重庆元石石墨烯技术开发有限责任公司 | Metallic nanowire-graphene bridge structural composite material and preparation method thereof |
| CN109827945A (en) * | 2019-02-28 | 2019-05-31 | 合肥工业大学 | A kind of preparation method of high SERS activity Ag/MXene-Ti3C2 composite material |
| CN111132533A (en) * | 2019-12-31 | 2020-05-08 | 浙江工业大学 | MXene/silver nanowire composite electromagnetic shielding film |
| CN111180701A (en) * | 2020-01-06 | 2020-05-19 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111223587A (en) * | 2020-01-16 | 2020-06-02 | 南开大学 | Dendritic layered self-assembled flexible conductive film and preparation method thereof |
| CN111341497A (en) * | 2020-03-13 | 2020-06-26 | 浙江大学 | Preparation method of silver nanowire-MXene composite transparent conductive film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114324514A (en) * | 2021-11-30 | 2022-04-12 | 南通大学 | PET-based flexible electrode and preparation method and application thereof |
| CN114883050A (en) * | 2022-04-26 | 2022-08-09 | 苏州博濬新材料科技有限公司 | Low-temperature sintering copper paste based on multi-conductive network structure filler and preparation method thereof |
| CN118639434A (en) * | 2024-08-14 | 2024-09-13 | 淮安金利达包装有限公司 | High-strength composite fiber material and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112652425A (en) | 2021-04-13 |
| CN111933351B (en) | 2021-06-08 |
| CN111933351A (en) | 2020-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111933351B (en) | Carbon nano tube composite transparent conductive film and preparation method thereof | |
| US10237974B2 (en) | Metal nanowire thin-films | |
| WO2018036428A1 (en) | Metal nanowire-oxidation-resistant material combined transparent conductive film and preparation therefor | |
| KR100621050B1 (en) | Transparent electro-conductive structure, process for its production, transparent electro-conductive layer forming coating fluid used for its production, and process for preparing the coating fluid | |
| TWI484065B (en) | Method for making flexible transparent conductive film | |
| JP5472889B2 (en) | Metal nanowire and transparent conductor including metal nanowire | |
| US9318230B2 (en) | Nanostructure dispersions and transparent conductors | |
| DE112007002342T5 (en) | Electrode forming composition and method of forming the electrode using the composition | |
| JPH10340629A (en) | Base board having transparent conductive film and its manufacture | |
| US20200062926A1 (en) | Metal-coated particles and resin composition | |
| CN110085350B (en) | Graphene-coated silver nanowire transparent conductive film and preparation method thereof | |
| KR101423169B1 (en) | A Method for Manufacturing of Shield Sheet for Preventing Electromagnetic Wave | |
| Testa et al. | Transparent flexible electrodes based on junctionless copper nanowire network via selective electroless metallization of electrospun nanofibers | |
| JP2011086786A (en) | Method of manufacturing light permeable electromagnetic shield material, and light permeable electromagnetic shield material | |
| CN104098277A (en) | Method for copperizing and silvering on surface of glass bead, and copperized and silvered glass bead | |
| KR101514743B1 (en) | The method for manufacturing patterned metal nanowire transparent electrode and the patterned metal nanowire transparent electrode thereby | |
| WO2017159537A1 (en) | Nanowire, process for producing nanowires, nanowire dispersion, and transparent electroconductive film | |
| KR100357946B1 (en) | Manufacturing process of transparent conductive layer | |
| CN109887646B (en) | Electrode and manufacturing method thereof | |
| JP2011086785A (en) | Method of manufacturing light permeable electromagnetic shield material, and light permeable electromagnetic shield material | |
| KR101006456B1 (en) | Method for fabrication of conductive film using sputtering and conductive film | |
| JP4600623B2 (en) | Method for forming electroless zinc oxide film | |
| CN110634593A (en) | Nano silver wire flexible transparent conductive film with low sheet resistance and excellent bending resistance and preparation method thereof | |
| KR101891222B1 (en) | Preparing method of metal nanotube for transparent electrode using electrospinning | |
| KR20090093565A (en) | Carbon nano tube transparent film and manufacturing method of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |