WO2011071885A2 - Compositions and methods for growing copper nanowires - Google Patents
Compositions and methods for growing copper nanowires Download PDFInfo
- Publication number
- WO2011071885A2 WO2011071885A2 PCT/US2010/059236 US2010059236W WO2011071885A2 WO 2011071885 A2 WO2011071885 A2 WO 2011071885A2 US 2010059236 W US2010059236 W US 2010059236W WO 2011071885 A2 WO2011071885 A2 WO 2011071885A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- acid
- solution
- cunws
- nanowires
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Definitions
- the present disclosure relates generally to the field of copper nanowires. Specifically, the present disclosure relates to copper nanowire structures, copper nanowire dispersion compositions, and methods of making said copper nanowires.
- Transparent conductors are used in a wide variety of applications, including low- emissivity windows, flat-panel displays, touch-sensitive control panels, solar cells and for electromagnetic shielding (Gordon 2000).
- the market for flat-panel displays alone is worth approximately $90 billion per year.
- Display makers prefer to use Indium Tin Oxide (ITO) as the transparent conductor because it can be applied at relatively low temperatures, and is easier to etch than materials with comparable conductivities and transmissivities (Gordon 2000).
- ITO films can be made with a sheet resistance of 10 ⁇ /sq transmit about 90% of visible light (Chopra 1983).
- ITO Indium is also a scarce element, present in the earth's crust at concentrations of only 0.05 parts per million (Taylor 1995).
- indium is also a scarce element, present in the earth's crust at concentrations of only 0.05 parts per million (Taylor 1995).
- Copper is 1000 times more abundant that indium or silver, and is 100 times less expensive.
- Films of copper nanowires could thus represent a low-cost alternative to silver nanowires or ITO for use as a transparent electrode.
- the methods described herein provide for the synthesis of CuNW s on the gram scale, and their transfer to a substrate to make transparent, conductive electrodes with properties comparable to ITO.
- the present disclosure relates to novel copper nanowire (CuNW) structures, which comprise a nanowire attached to a spherical nanoparticle, a novel dispersion of CuNWs in which they are free from aggregation, and methods of synthesizing nanowires to produce said dispersion at a large scale.
- CuNW copper nanowire
- a copper nanowire comprising a copper stick attached to a spherical copper nanoparticle.
- the copper nanowires further comprise a protective film.
- a dispersion of copper nanowires comprising copper nanowires (CuNWs) and a dispersion solution, wherein the CuNW s are substantially free from aggregation
- CuNWs copper nanowires
- CuNWs copper nanowires
- a conductive film comprising a network of copper nanowires (CuNWs) is described, said conductive film having a sheet resistance of less than about 10,000 ⁇ /sq, preferably less than about 1000 ⁇ /sq, more preferably less than 100 ⁇ /sq, and most preferably less than 30 ⁇ /sq.
- the conductive film has a transparency greater than about 60%, preferably greater than 70%, and most preferably greater than 85%.
- a method of making a conductive film comprising a network of copper nanowires (CuNWs), said conductive film having a sheet resistance of less than about 10,000 ⁇ /sq, said method comprising printing a CuNWs dispersion onto a substrate.
- the sheet resistance is less than about 1000 ⁇ /sq, more preferably less than 100 ⁇ /sq, and most preferably less than 30 ⁇ /sq
- the conductive film has a transparency greater than about 60%, and transparencies greater than 60%>, preferably greater than 70% and most preferably transparencies greater than 85%.
- FIGs 1 A- IB show images of a scale up reaction of the copper nanowire synthesis and the SEM image of copper nanowires reacted at 80°C for 60 minutes.
- FIG 1C is an image of the copper nanowires.
- the inset is a close-up of the copper nanowires, scale bar is 200 nm.
- FIGs 3A and 3B are from a CuNW film that are 38% and 67% transparent, respectively, having sheet resistances of 1.5 ⁇ /sq and 61 ⁇ /sq, respectively.
- Figures 3C & D show corresponding camera images of CuNW films 35 mm in diameter to visually demonstrate the difference in transparency between these copper nanowire films.
- FIG 4A shows a plot of %Transmittance versus Sheet resistance in ⁇ /sq showing thin films composed of the as synthesized CuNWs (filled circles), AgNWs (triangles), ITO (stars), and Carbon Nanotubes (CNTs) (open circles). Error bars show one standard deviation of the CuNW film's sheet resistance.
- FIG 4B shows a plot of sheet resistance versus time in days showing the stability of the CuNW film.
- FIG 5 shows CuNW diameter and length versus EDA concentration, respectively.
- FIG 5A shows CuNW diameter (nrn) versus EDA concentration (moles L “1 ). Error bars show one standard deviation for 16- 40 measurements.
- FIG 5B shows CuNW length ( ⁇ ) versus EDA concentration (moles L "1 ). Error bars show one standard deviation for 7-10 measurements.
- FIG. 7 shows a schematic of an embodiment for the synthesis of longer, well-dispersed, copper nanowires.
- Figure 8 shows the effect of surfactant on the generation of CuNWs in accordance with one embodiment of the present disclosure.
- FIGs 8A and 8B are graphs showing the PVP to water ratio added to the reaction after the reaction mixture is removed from the hot water bath and their corresponding effect on CuNW diameter and length, respectively. These reactions were completed using a 20 mL small-scale reaction.
- FIGs 9A and 9B are graphs showing the amount of time a reaction spends heating up versus diameter and length, respectively.
- FIGs 10A and 10B are graphs showing the effect the amount of time the reaction sat at room temperature versus nanowire diameters and lengths, respectively, for three different reaction temperatures.
- FIG 11 shows that nanowires grown to have the same width but different lengths enable a width- independent analysis of the effects of nanowire length on the conductivity of nanowire films.
- FIG 1 IB shows a plot of sheet resistance as a function of wire density.
- FIG 11C shows a logarithmic plot of sheet conductance versus nL 2 - 5.71, where 5.71 is nL 2 required for percolation predicted by theory.
- the solid line with a slope of 1.33 shows the relationship between conductance and nL 2 predicted by percolation theory.
- Figure 12 shows transmittance versus sheet resistance of copper nanowire, silver nanowire, carbon nanotube, and indium tin oxide films.
- the wavelength at which the transmittance was measured is 500 nm.
- Figure 13 shows the transmittance spectrum of copper nanowire, silver nanowire, and indium tin oxide films.
- Figure 14 shows a film of copper nanowires with a conductivity of 9.71 ⁇ 7.4 ⁇ /sq and a transmittance of 85%.
- Figure 15 is a dark- field microscope image showing scattering of light from the copper nanowires (long copper-colored strands), as well as some circular defects or particles on the substrate.
- Figure 16 is a plot of sheet resistance versus number of bends showing no change in CuNW conductivity after 1000 bends.
- Figure 17 plots the conductivity of nanowire films coated onto glass with a Meyer Rod.
- Figure 18 is an SEM image of Cu nanowires coated with nickel.
- Figure 19 shows the calculated upper bound for the transmittance of conducting network of nanowires with different lengths and widths.
- the present disclosure relates to a novel copper nanowire (CuNW) structures, which comprise a nanowire attached to a spherical nanoparticle, a novel dispersion of CuNWs in which they are free from aggregation, and methods of synthesizing nanowires to produce said dispersion at a large scale.
- Transparent electrodes made from these new, well-dispersed copper nanowires perform at the same level as silver nanowires, producing electrodes with sheet resistances under 10,000 ⁇ /sq, preferably less than about 1000 ⁇ /sq, more preferably less than 100 ⁇ /sq, and most preferably less than 30 ⁇ /sq, and transparencies greater than 60%, preferably greater than 70% and most preferably transparencies greater than 85%.
- capping agent includes those compounds that are understood by one skilled in the art to alter the assembly of atoms of the growing structure into anisotropic states.
- dispersions of copper wires having the appropriate characteristics are preferably produced by separating the seed nucleation and nanowire growth steps into two different reaction parts of the reaction. Specifically, after the seeds form or otherwise nucleate, a surfactant solution may be added to the reaction to stabilize the nanowires during their growth. Preferably, the temperature of the solution is also lowered during the growth phase to produce longer nanowires.
- the present description relates to a method for producing CuNWs on a gram scale, said method comprising, consisting of, or consisting essentially of mixing a copper (II) ion source, at least one reducing agent, at least one copper capping agent, and at least one pH adjusting species to form a solution; stirring and heating the solution for time necessary to reduce the copper (II) ions; collecting formed CuNWs; and washing formed CuNWs with a wash solution.
- a copper (II) ion source at least one reducing agent, at least one copper capping agent, and at least one pH adjusting species
- a method for producing CuNWs on a gram scale can comprise, consist of, or consist essentially of reducing a solution containing Cu(NOs)2 and at least one component selected from the group consisting of hydrazine, EDA, NaOH and combinations thereof; stirring and heating the solution at 80°C for at least 60 minutes until the solution turns from a royal blue color to a reddish brown color, indicating the CuNWs have been formed; and washing the formed CuNWs with hydrazine.
- a second aspect relates to a method of producing dispersions of CuNW s comprising, consisting of, or consisting essentially of mixing a copper (II) ion source, at least one reducing agent, at least one copper capping agent, and at least one pH adjusting species to form a first solution; maintaining the first solution for time and temperature necessary to reduce the copper (II) ions; adding a second solution comprising water and at least one surfactant to create a mixture; and maintaining the mixture at time and temperature necessary to form CuNWs.
- the method of producing dispersions of CuNWs on the gram scale comprises, consists of, or consists essentially of mixing a copper ( ⁇ ) ion source, at least one reducing agent, at least one copper capping agent, and at least one pH adjusting species to form a first solution; stirring and heating the first solution for time necessary to reduce the copper (II) ions; adding a second solution comprising water and at least one surfactant to create a mixture; and cooling the mixture for time necessary to form CuNWs.
- the method of producing dispersions of CuNWs on the gram scale comprises, consists of, or consists essentially of mixing a copper (II) ion source, at least one reducing agent, at least one copper capping agent, and at least one pH adjusting species to form a first solution; stirring and heating the first solution for time necessary to reduce the copper (II) ions; removing the first solution from the heat; adding a second solution comprising water and at least one surfactant to create a mixture; and cooling the mixture for time necessary to form CuNWs.
- a copper (II) ion source at least one reducing agent, at least one copper capping agent, and at least one pH adjusting species
- the method of producing dispersions of CuNWs comprises, consists of, or consists essentially of reducing a solution containing a copper (II) ion source, at least one reducing agent, at least one copper capping agent, and at least one pH adjusting species species to form a first solution; stirring and heating the first solution at temperature in a range from about 60°C to about 100°C for time necessary to reduce the copper (II) ions; removing the first solution from the heat and adding a second solution comprising water and at least one surfactant to create a mixture; and placing the mixture in an ice bath for time necessary to form CuNWs.
- the method of producing dispersions of CuNWs comprises, consists of, or consists essentially of reducing a solution containing Cu N0 3 )2 and at least one component selected from the group consisting of hydrazine, EDA, NaOH and combinations thereof to form a first solution; stirring and heating the first solution at 80°C for at least five minutes until the first solution generates a darker hue color; removing the first solution from the heat and adding a second solution comprising water and at least one surfactant, e.g., PVP, to create a mixture; and placing the mixture in an ice bath for at least one hour until the mixture turns a light pink color, indicating CuNWs have been formed.
- a surfactant e.g., PVP
- the formed CuNWs can be collected and washed. Collecting can be effectuated by allowing the mixture to settle, for example for a period ranging from 10 to 15 minutes, wherein the CuNWs are extracted from a layer floating on the surface of the mixture; and washing can be effectuated using an aqueous solution comprising an amine species, a surfactant, or combinations thereof.
- At least one surfactant is preferentially not added to the first solution until after a time wherein reduction of the copper (II) ions has been effectuated, e.g., after stirring and heating the first solution at temperature in a range from about 60°C to about 100°C.
- the first solution is agitated for at least 20 seconds after the addition of each component thereto. In other embodiments, the first solution is stirred at about 200 rpm.
- the washing and collecting comprise, consist of, or consist essentially of dispersing the formed CuNWs by vortexing and centrifuging the wash solution, e.g., at 2000 rpm, for at least 15 minutes. In certain other embodiments, the washing of the formed CuNWs is repeated several times.
- the second solution comprising the water and the surfactant can be mixed prior to the addition to the solution, or alternatively not mixed prior to the addition to the solution.
- mixtureed corresponds to homogeneity upon combination of the surfactant and water, wherein the solubilized surfactant is homogeneously distributed in the second solution. Accordingly, “not mixed” corresponds to anything less than solution homogeneity.
- Copper (II) ion sources contemplated herein include, but are not limited to, copper nitrate, copper sulfate, copper nitrite, copper sulfite, copper acetate, copper chloride, copper bromide, copper iodide, copper phosphate, copper carbonate, and combinations thereof.
- the copper (II) source comprises copper (II) nitrate.
- Reducing agents contemplated include, but are not limited to, hydrazine, ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, oxalic acid, formic acid, phosphites, phosphorous acid, sulfites, sodium borohydride, and combinations thereof.
- the reducing agent comprises hydrazine.
- Copper capping agents contemplated herein include, but are not limited to, triethylenediamine; ethylenediamine (EDA); propane-l,3-diamine; butane- 1,4-diamine; pentane-l,5-diamine; ethyl enediaminetetraacetic acid (EDTA), l,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), glycine, ascorbic acid, iminodiacetic acid (IDA), nitrilotriacetic acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, gallic acid, boric acid, acetic acid, ace
- pH adjusting species include, but are not limited to, sodium hydroxide; potassium hydroxide; cesium hydroxide; rubidium hydroxide; magnesium hydroxide; calcium hydroxide; strontium hydroxide; barium hydroxide; and compounds of the formula NR R ⁇ R'OH, wherein R 1 , R 2 , R 3 and R 4 may be the same as or different from one another and are selected from the group consisting of hydrogen, straight- chained or branched Ci-Ce alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), and substituted or unsubstituted C6-C 10 aryl, e.g., benzyl.
- the pH adjusting species comprises NaOH, KOH, or a combination of NaOH and KOH.
- Surfactants contemplated herein include, but are not limited to, water soluble polymers such as polyethylene glycol (PEG), polyethylene oxide (PEO), polypropylene glycol, polyvinyl pyrrolidone (PVP), cationic polymers, nonionic polymers, anionic polymers, hydroxyethylcellulose (HEC), acrylamide polymers, poly( acrylic acid), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na CMC), hydroxypropylmethylcellulose, polyvinylpyrrolidone (PVP), BIOCARETM polymers, DOWTM latex powders (DLP), ETHOCELTM ethylcellulose polymers, KYTAMERTM PC polymers, METHOCELTM cellulose ethers, POLYOXTM water soluble resins, SoftCATTM polymers, UCARETM polymers, gum arabic, sorbitan esters (e.g., sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostea
- surfactants contemplated include: cationic surfactants such as cetyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium bromide (HTAB), cetyltrimethylammonium hydrogen sulfate; anionic surfactants such as sodium alkyl sulfates, eee.g., sodium dodecyl sulfate, ammonium alkyl sulfates, alkyl (Cio-Cig) carboxylic acid ammonium salts, sodium sulfosuccinates and esters thereof, e.g., dioctyl sodium sulfosuccinate, alkyl (Cio-Cig) sulfonic acid sodium salts, and the di-anionic sulfonate surfactants DowFax (The Dow Chemical Company, Midland, Mich., USA); and nonionic surfactants such as t-octylphenoxypolyethoxyethanol (
- the CuNW s may be stored in the solution comprising a hydrazine, a surfactant, an alcohol, or combinations thereof.
- Alcohols contemplated herein include straight chained or branched Ci-Ce alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol.
- the storage solution comprises, consists of, or consists essentially of: dispersed CuNW s, water, and hydrazine; dispersed CuNWs, water, hydrazine and PVP; or dispersed CuNWs, water, and ethanol.
- the CuNW dispersion comprises, consists of, or consists essentially of CuNWs and a storage solution, wherein the CuNW s are substantially free of aggregation, and wherein the storage solution comprises a species selected from the group consisting of hydrazine, at least one surfactant, at least one alcohol, water, and a combination thereof.
- substantially free corresponds to less than about 5 wt% of the total weighed amount of CuNW s are aggregated, preferably less than about 2 wt%, and most preferably less than 1 wt% of the total weighed amount of CuNWs are aggregated.
- aggregated refers to the formation of clumps of nanowires due to their mutual van der Waals attraction Such clumps may consist of as few as two nanowires, and as many as 10 12 nanowires or more. Formation of clumps is generally not reversible in this context, and thus is preferably prevented in order to ensure the film consists of a network of individual wires, rather than clumps.
- Clumps reduce the transmittance of films, and do not improve the conductivity. Such clumps can easily be identified in a film with a dark field optical microscope, or a scanning electron microscope. It is preferred that the nanowire film contain a minimal amount of clumps in order to reach properties comparable with ⁇ ( ⁇ 30 ⁇ /sq, >85% transmittance).
- a novel copper structure comprising a nanowire stick attached to a spherical nanoparticle.
- the novel copper structure has a first end and a second end that is generated using the method according to the present disclosure, wherein the CuNW comprises a length of about 1 to 500 microns, a diameter of about 20 to 300 nm, and a spherical particle of about 30 to 1000 nm attached to either the first end or the second end.
- the nanowire structure, dispersion and production methods described herein have many practical applications including, but not limited to, (1) the ability to coat the nanowires directly from solution onto both rigid and flexible substrates to produce transparent conductive films that can subsequently be patterned; (2) the ability to use printing processes with conductive inks incorporating copper nanowires to make conductive metal lines, shapes, characters, patterns, etc.; and (3) the ability to use the copper nanowires as an additive to pastes, glues, paints, plastics, and composites to create electrically conductive materials.
- another aspect relates to a method further of printing the formed CuNWs onto substrates for use as conductive films.
- the formed CuNW s may be coated directly from solution onto rigid substrates, flexible substrates, or combinations thereof, to produce conductive films that can be subsequently patterned.
- the conductive films are transparent and made from the CuNW s prepared using the processes described herein, wherein said transparent conductive films perform similarly to silver nanowires by having sheet resistances less than about 10,000 ⁇ /sq, preferably less than about 1000 ⁇ /sq, more preferably less than 100 ⁇ /sq, and most preferably less than 30 ⁇ /sq, and transparencies greater than about 60%, preferably greater than about 70%, and most preferably greater than about 85%.
- any coating method including those that are used in web coating or roll-to-roll processes, that involves deposition of material from a liquid phase onto a substrate can be applied to making films of nanowires.
- coating processes include the Mayer rod process, air-brushing, gravure, reverse roll, knife over roll, metering rod, slot die, immersion, curtain, and air knife coating.
- a method of producing a conductive copper-containing film is described, said method comprising depositing a layer of CuNWs from a CuNW dispersion onto a substrate using a coating process.
- the film can comprise, consist of or consist essentially of a network of CuNW s or a network of CuNW s and at least one supportive material, wherein the supportive material includes, but is not limited to, cellulose materials, glues, polymeric materials, or general overcoat materials, e.g., oxygen and moisture impervious barriers, as readily known by one skilled in the art.
- the sheet resistance of the copper-containing film is less than about 10,000 ⁇ /sq, more preferably less than about 1000 ⁇ /sq, even more preferably less than 100 ⁇ /sq, and most preferably less than 30 ⁇ /sq.
- a "network" corresponds to an arrangement of wires such that the wires are interconnected.
- a method of producing a conductive, transparent copper-containing film comprising depositing a layer of CuNWs from a CuNW dispersion onto a substrate using a coating process.
- the film can comprise, consist of or consist essentially of a network of CuNW s or a network of CuNW s and at least one supportive material, wherein the supportive material includes, but is not limited to, cellulose materials, glues, polymeric materials, or general overcoat materials, as readily known by one skilled in the art.
- the sheet resistance of the copper-containing film is less than about 10,000 ⁇ /sq, more preferably less than about 1000 ⁇ /sq, even more preferably less than 100 ⁇ /sq, and most preferably less than 30 ⁇ /sq, and the transparency greater than about 60%, preferably greater than about 70%), and most preferably greater than about 85%.
- the copper-containing films preferably are used as transparent electrodes.
- a "film" of nanowires corresponds to a thin covering of nanowires on a surface.
- the film may consist solely of nanowires, or of nanowires with supportive materials.
- the nanowires preferably form an interconnecting network within the film.
- any method that can be used to pattern deposition of material can be used to pattern films of nanowires including, but not limited to, Ink Jet, Gravure, Screen, and other printing processes.
- nanowires can be suspended in an organic or aqueous solution at an appropriate concentration to make a conducting film. Nanowires can also be suspended in photocurable monomer mixtures and selectively cured with UV light to create a pattern of conductive material. Nanowires can also be patterned with subtractive processes. For example, after casting a film of nanowires onto a surface, specific areas can be chemically etched away or a sticky rubber stamp can be applied to remove the nanowires.
- the method for recycling ingredients from a prior production of CuNWs to produce CuNWs on a gram scale comprises, consists of, or consists essentially of collecting the CuNW s from the mixture; and reusing the solution comprising the basic species, wherein the copper (II) ion source and optionally additional basic species are replenished to produce new solution.
- the rate of oxidation of the CuNWs may be reduced by annealing or by forming protecting films on the CuNWs.
- Copper is widely used in the chemical and electronics industry, and many techniques have been developed to protect copper from oxidation.
- Copper can also be coated or alloyed with nickel, gold, tin, zinc, silver, and other metals to prevent corrosion. Alloying with nickel has the additional benefit of conferring a silvery color to the copper, which may be useful for applications such as displays and e-readers, where a copper tint is undesirable. Copper films must also be protected from mechanical damage. This can be accomplished by applying a thin layer of protective polymer or other coating over the nanowire film. This coating can have the added benefit of improving the adhesion of the nanowires to the substrate. Examples of such coatings include Teflon, cellulose acetate, ethylcellulose and acrylates.
- a copper-containing film comprising, consisting of, or consisting essentially of a network of CuNW s and at least one supportive material is processed to remove the supportive material to yield a network of CuNW s.
- a method of annealing a copper-containing film comprising a network of CuNWs and at least one supportive material is described, said method comprising heating the copper- containing film in a reducing atmosphere at a temperature that removes the supportive material from the copper-containing film to yield a network of CuNWs.
- the reducing atmosphere comprises hydrogen gas and the anneal is carried out at temperature in a range from about 100°C to about 500°C, preferably about 350°C, for time in a range from about 0.1 min to about 180 min, preferably about 20 min to about 40 min, and most preferably about 30 min.
- Copper nanowires were synthesized by reducing Cu(NOs)2 with hydrazine in an aqueous solution containing NaOH and, ethylenediamine (EDA).
- EDA ethylenediamine
- Figure 1 2000 mL of 15 M NaOH, 100 mL of 0.2 M Cu(N0 3 ) 2 , 30 mL EDA, and 2.5 mL of 35 wt% hydrazine were added to the reaction flask and swirled by hand for 20 seconds after each addition to mix the reactants. This solution was heated at 80 °C and stirred at 200 rpm for 60 minutes.
- Figure 1C shows a scanning electron microscope (SEM, FEI XL30) image of the reaction product, consisting of CuNWs with a diameter of 90 ⁇ 10 nm.
- the inset image shows a close up of the wires, in which it appears spherical nanoparticles are attached to one end of the nanowires.
- EDA amine species
- wires did not grow. Instead, only spheres with diameters ranging from 125-500 nm were present after 1 hr.
- the amine groups of EDA may bind to the surface of copper nanostructures in solution.
- the CuNWs may be sonicated in an aqueous solution containing 3 wt % of hydrazine solution and 1 wt% PVP. This solution was gently poured on top of 640 ml of an aqueous solution of 10 wt% PVP in a 1000 ml graduated cylinder. The Cu aggregates that were not dispersed during sonication settled to the bottom of the cylinder, leaving the well-dispersed NWs suspended in solution.
- the well-dispersed CuNWs were filtered onto 0.6 gm polycarbonate membranes, and printed onto glass microscope slides coated with Aleene's Clear Gel Glue.
- a thin film (8 ⁇ 0.1 ⁇ , Veeco Dektak 150) of glue was deposited onto the slides with a spin coater (Air Control Spin Coat Hood), and allowed to dry for one hour so that it hardened but remained sticky.
- the CuNW filtrate on the membrane was then put into contact with the sticky film by hand, and the membrane was peeled away, leaving the CuNWs on the clear glue.
- Figures 3C & D show corresponding camera images of CuNW films 35 mm in diameter to visually demonstrate the difference in transparency between these copper nanowire films, as well as their overall uniformity.
- FIG. 6A and B are images comparing a film of copper nanowires with silver nanowires that illustrate that copper nanowires cluster into aggregates while silver nanowires are uniformly dispersed. Accordingly, a key requirement to optimizing the properties of copper nanowire transparent conducting films is forming a well-dispersed suspension of copper nanowires prior to assembling them into a film to maximize the open area of the film, and ensuring that all copper nanowires in the film contribute to the conductivity of the film.
- a 1000 mL round bottom flask was cleaned with nitric acid and rinsed several times to make sure it was clean. The flask was then allowed to dry in an oven set to 80°C. Once dry, the flask was removed from the oven and allowed to cool to room temperature before being used.
- the CuNWs were synthesized by adding NoOH (200 mL, 15 M), Cu(N0 3 ) 2 (10 mL, 0.1 M), ethylenediamine (1.5 mL), and hydrazine (0.25 mL, 35 wt%) to the 1000 mL round bottom flask. This solution was swirled by hand for 20 seconds after each addition to ensure everything was mixed together. The solution was then heated at 80 C for approximately five (5) minutes while stirring at 200 rpm. When the solution is ready to be removed from the heat, it will have a darker hue to it, but it will not have a brownish/red color.
- the reaction mixture may be transferred to a beaker and allowed to settle for 10-15 minutes.
- the CuNWs float to the surface of the mixture and can be scooped into a centrifuge tube containing 10 mL of an aqueous solution of hydrazine (3 wt%) and PVP (10 wt%).
- the solution can be decanted and 20 mL of the same hydrazine/PVP can be added to the CuNW s.
- the wires were then vortexed to disperse the wires before being centrifuged at 2000 rpm for 15 minutes. After being centrifuged, the wires can be further cleaned by repeating this process, e.g., one, two, three, or multiple other times. Once clean, the CuNWs can be stored in the same hydrazine/PVP solution.
- the concentration of ingredients, reaction temperature, and reaction times can vary to produce nanowires of similar dimensions and dispersion, or produce nanowires of different dimensions.
- Table 1 below shows a nonlimiting range of reactants and conditions that produce nanowires in accordance with the present disclosure.
- Table 1 Minimum and Maximum weight percent of each reactant, temperature, and time needed to produce copper wires
- the reaction may be performed in a concentrated solution of NaOH for the formation of CuNW s.
- the preferred amount of NaOH for a 20 mL scale reaction is in a range from about 9.6 g to about 12 g.
- a blue precipitate presumably Cu(OH) 2
- the concentration of NaOH exceeds 15 M
- the NaOH becomes increasingly difficult to dissolve. If there are solid NaOH pieces within the solution, the reaction will precipitate prematurely and produce only particles.
- KOH and other strong bases will also be suitable for raising the pH of the solution and facilitating the reduction of copper by hydrazine.
- Hydrazine is the preferred reducing agent to reduce the copper(II) ions, e.g., Cu(N0 3 )2, to copper nanowires.
- the preferred amount of hydrazine is greater than about 8.79 ⁇ g for the 20 mL scale reaction. Below 8.79 ⁇ g the reaction does not produce as many CuNW s and below 5.3 ⁇ g the reaction does not always proceed. When using more than 8.79 ⁇ g of hydrazine per reaction, the reaction begins to proceed more quickly and more particles are generated.
- Copper(II) nitrate is the preferred copper (II) ion source and is preferably in a range from about 5.8 mg to about 23.3 mg for a 20 mL scale reaction. If there is not enough copper (II) nitrate present, the hydrazine will reduce it to particles and no wires will form. At 5.8 mg of copper(II) nitrate, the majority of the precipitate is particles but a few wires are present. When the copper(II) nitrate is increased to 34.9 mg, the solution turns yellow and when observed under a dark field optical microscope, the yellow precipitate appears to be small particles.
- FIGs 8A and 8B show that the dimensions of copper nanowires are not strongly dependent on the concentration of PVP. However, there is an optimal PVP concentration, approximately 2-4 mg/ml, at which the width of the copper nanowires is minimized, and the length is maximized. All concentrations of PVP above 2 mg/ml produce nanowires that are well-dispersed.
- FIGs 9A and 9B show the effect of time on the diameter and length of CuNW s, respectively. These reactions were completed with a 20 mL, small-scale reaction and the amount of time a reaction spends heating up versus diameter and length, respectively, were graphed.
- FIGs 1 OA and 1 OB also completed with a 20 mL, small-scale reaction, show the effect the amount of time the reaction sat at room temperature versus nanowire diameters and lengths, respectively, for three different reaction temperatures.
- the reaction sat at room temperature because the reactions done at 50 and 60°C did not precipitate in the ice.
- the 80°C reactions were placed in the ice for one hour and then removed for the duration of the experiments.
- Table 2 shows a table presenting a cost comparison of the ingredients in the syntheses of silver and copper nanowires. Notably, the cost of copper nitrate comprises only 4.2 % of the cost of the ingredients of making CuNW s.
- Table 2 Cost comparison of the reactants required to synthesize Cu and Ag nanowires.
- Inexpensive polymer tanks exceeding 10,000 L are commercially available and are likely suitable for carrying out the reaction at scales exceeding 1 kg.
- stirring with a magnetic stir bar can be replaced by a mechanically driven, propeller type, stirrer. Heating can be accomplished with an immersion type heater.
- the nanowires can be removed from the top of the reaction with a skimming or suction process. Centrifugation can be replaced with filtration, settling, or other colloidal separation processes to wash the wires.
- the unreacted ingredients can be drained from the vessel and sent through a number of separation processes (e.g. filtration) for reuse.
- FIG 12 shows that both the improved length and the reduced clumping result in an improvement of the properties of copper nanowire films to be on par or better than films of silver nanowires.
- films of indium tin oxide (ITO) are more transparent in the visible region of the electromagnetic spectrum, films of copper nanowires are much more transparent at telecommunication wavelengths ( ⁇ 1500 nm, see FIG 13).
- FIG 14 shows a circular film of copper nanowires that has been formed by filtering the copper nanowires, and printing the wires onto a piece of glue.
- FIG 15 is a dark field microscope image showing scattering of light from the nanowires as well as from particles/dust/defects on the substrate. Note that the nanowires are present as individual wires rather than clumps. This film has a conductivity of 10 ⁇ /sq and a transmittance of 85%. We also found that spraying the nanowires with an airbrush onto a substrate results in films with similar properties.
- Flasks and stir bars were cleaned with concentrated nitric acid, thoroughly rinsed with DI water, and dried in an 80°C oven before use. Once dry, the flasks were allowed to cool to room temperature before any reactants were added.
- CuNWs were synthesized by adding NaOH (20 mL, 15M), Cu(N0 3 ) 2 (1 mL, 0.1M), EDA (0.15 mL), and hydrazine (0.025 mL, 35 wt%) to a 50 mL round bottom flask. This mixture was swirled by hand for 5 seconds after each addition to mix the reactants. The solution was then heated at 80°C and stirred at 200 rpm for approximately 3 minutes. After the reaction, the solution was poured into a 50 mL centrifuge tube and a PVP and water solution (20 mg PVP in 5 mL of water) was gently added to the top. The reaction solution and PVP solution were not mixed before being put in an ice bath.
- the solution was allowed to finish reacting in the ice for 1 hour before being transferred to a beaker.
- the solution was allowed to settle, allowing the CuNWs to float to the top of the solution before being scooped into 15 mL of hydrazine (3 wt%), PVP (1 gram), and water (97 mL).
- the solution was centrifuged at 2000 rpm for 20 minutes, and the supernate was decanted from the nanowires.
- the wires were then dispersed in the aqueous solution of hydrazine and PVP by vortexing for 30 seconds, and then centrifuged and decanted for 3 more cycles.
- the CuNWs were stored in the 3 wt% hydrazine/PVP solution at room temperature under an argon atmosphere to minimize oxidation.
- the dispersed CuNWs were printed onto a substrate using the Mayer rod printing method.
- a printing formulation was prepared by adding 3 grams of the 5 wt% ethyl cellulose solution to a 20 mL scintillation vial. Then 0.25 grams of ethyl acetate, 0.5 grams isopropanol, 1 mL toluene, and 0.5 grams of pentyl acetate were added to the vial, wherein after each addition the solution was vortexed for 30 seconds to ensure good mixing.
- the resulting formulation comprises copper nano wires ready for printing.
- a clipboard was taped to a flat service with double sided tape.
- a glass microscope slide or piece of plastic was then placed in the clip of the clip board.
- 25 ⁇ L of the copper nanowire formulation was then evenly spread in a line at the top of the glass slide.
- a Mayer Rod with a specified wire gauge was placed between the copper nanowire line and the clip and then quickly pulled to the bottom of the glass slide.
- the amount of pressure applied to the Mayer Rod was minimal.
- the film was then allowed to dry in air.
- the transmittance of the film can be measured once the film is dry in order to gauge how transparent it will be once the process is finished, keeping in mind that once the ethyl cellulose is burned off the transmittance will increase.
- the thickness of the film can be changed by 1) using a different Mayer Rod with a different wire gauge or 2) diluting/concentrating the copper nanowire formulation.
- the glass slides with the films were cut into pieces of -0.5 inches.
- the glass pieces were then placed in a tube furnace, under hydrogen flowing at 250 mL/min for 10 minutes. After the system was flushed with hydrogen the furnace was brought up to 350°C for 30 minutes. After 30 minutes the system was allowed to cool to room temperature before removing the glass pieces from the tube. Finally the sheet resistance and final transmittance were measured and recorded. The results are illustrated in FIG 17.
- Nickel Coating Reaction The CuNWs, stored in 3 wt% hydrazine and 4 wt% PVP are centrifuged and washed twice with a 4 wt% PVP solution. Wires are spun at 2000 rpm for 5 minutes. Wires are concentrated into a 4 wt% PVP solution.
- Copper nanowires are coated by adding the following reactants, listed by order, into a disposable lOmL vial:
- Ni(N0 3 )2-6H 2 0 diluted to 2mL H 2 0.
- Ni:Cu reaction 1570 iL 0.1M Ni(N0 3 ) 2 -6H 2 0 and 430 iL DI water were added to the vial.
- the vial was then heated in a 55°C water bath with a 600 rpm stir rate for 40 minutes.
- the reaction is transferred to a centrifuge tube.
- a 3 wt% hydrazine, 4 wt% PVP solution was added to precipitate PVP and aggregate the wires.
- the sodium hydroxide was decanted, and a 3 wt% hydrazine, 4 wt% PVP solution was added again.
- the reaction was thoroughly vortexed to disperse the wires.
- the reaction is centrifuged twice (2000 rpm, 5 min) and washed twice with a solution of 3 wt% hydrazine, 4 wt% PVP and stored in room temperature.
- Ni and Cu do alloy. These characteristics make Ni a promising material for coating of the Cu Nanowires. We have been able to obtain copper nanowires with Ni sheaths, as seen in FIG 18.
- Percolation is the minimum density of nanowire required to make a conducting network. It has been found theoretically that the percolation of a network of sticks depends on the density N and length L of the sticks, as given by equation 1 :
- Figure 19 illustrates that better transmittances are obtained with thinner, longer nanowires.
- the width of the nanowires is decreased below 50 nm, the resistivity of the copper will increase due to scattering of electrons off the sides of the wires. Furthermore, the wires will lose their stiffness and become more like noodles than sticks which will decrease their effective length and thus the performance of the films.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Laminated Bodies (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2010328361A AU2010328361A1 (en) | 2009-12-07 | 2010-12-07 | Compositions and methods for growing copper nanowires |
JP2012543198A JP2013513220A (en) | 2009-12-07 | 2010-12-07 | Compositions and methods for growing copper nanowires |
SG2012041968A SG181565A1 (en) | 2009-12-07 | 2010-12-07 | Compositions and methods for growing copper nanowires |
EP10836521.4A EP2510524A4 (en) | 2009-12-07 | 2010-12-07 | Compositions and methods for growing copper nanowires |
CN2010800628951A CN102792385A (en) | 2009-12-07 | 2010-12-07 | Compositions and methods for growing copper nanowires |
US13/514,176 US20130008690A1 (en) | 2009-12-07 | 2010-12-07 | Compositions and methods for growing copper nanowires |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US26724809P | 2009-12-07 | 2009-12-07 | |
US61/267,248 | 2009-12-07 | ||
US37724110P | 2010-08-26 | 2010-08-26 | |
US61/377,241 | 2010-08-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2011071885A2 true WO2011071885A2 (en) | 2011-06-16 |
WO2011071885A3 WO2011071885A3 (en) | 2011-10-13 |
Family
ID=44146138
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/059236 WO2011071885A2 (en) | 2009-12-07 | 2010-12-07 | Compositions and methods for growing copper nanowires |
Country Status (9)
Country | Link |
---|---|
US (1) | US20130008690A1 (en) |
EP (1) | EP2510524A4 (en) |
JP (1) | JP2013513220A (en) |
KR (1) | KR20120115298A (en) |
CN (1) | CN102792385A (en) |
AU (1) | AU2010328361A1 (en) |
SG (2) | SG10201408043RA (en) |
TW (1) | TWI508922B (en) |
WO (1) | WO2011071885A2 (en) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102601382A (en) * | 2012-03-27 | 2012-07-25 | 苏州冷石纳米材料科技有限公司 | Method for massively preparing overlength copper nanowires |
WO2013019020A2 (en) * | 2011-07-29 | 2013-02-07 | Lg Innotek Co., Ltd. | Nano-wire and method for manufacturing the same |
WO2013086139A1 (en) * | 2011-12-07 | 2013-06-13 | Duke University | Synthesis of cupronickel nanowires and their application in transparent conducting films |
JP2013159809A (en) * | 2012-02-03 | 2013-08-19 | Unitika Ltd | Method for producing copper fine particle, copper fine particle obtained by the method, and coating material using the copper fine particle |
KR101334601B1 (en) * | 2011-10-11 | 2013-11-29 | 한국과학기술연구원 | Metal nanowire with high linearity, fabrication method of the same and transparent conducting film comprising the same |
WO2013187384A1 (en) * | 2012-06-11 | 2013-12-19 | ユニチカ株式会社 | Fibrous copper microparticles and method for manufacturing same |
WO2014004712A1 (en) * | 2012-06-28 | 2014-01-03 | Nthdegree Technologies Worldwide Inc. | Systems and methods for fabrication of nanostructures |
JP2014037602A (en) * | 2012-08-20 | 2014-02-27 | Furukawa Electric Co Ltd:The | Method for producing copper nanowire, copper nanowire and application thereof |
WO2014063769A1 (en) * | 2012-10-25 | 2014-05-01 | Merck Patent Gmbh | Processing of copper-based nanowires for transparent conductors |
JP2014118590A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Fibrous silver fine particle aggregate |
JP2014118589A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Coated fibrous copper fine particle aggregate |
JP2014133946A (en) * | 2012-12-14 | 2014-07-24 | Unitika Ltd | Aggregate of fibrous copper fine particle, manufacturing method of aggregate of fibrous copper fine particle |
US20140299821A1 (en) * | 2011-11-03 | 2014-10-09 | Bayer Intellectual Property Gmbh | Method for producing a metal nanoparticle dispersion, metal nanoparticle dispersion, and use of said metal nanoparticle dispersion |
CN104475755A (en) * | 2014-12-30 | 2015-04-01 | 山西森达源科技有限公司 | Preparation method of spheroidal ultrafine silver powder for front surface of solar cell |
WO2015120960A1 (en) * | 2014-02-11 | 2015-08-20 | Merck Patent Gmbh | Green chemistry method of making copper nanowires |
WO2016122412A1 (en) | 2015-01-30 | 2016-08-04 | Nanyang Technological University | Conductive paste, method for forming an interconnection and electrical device |
EP3197901A1 (en) * | 2014-09-26 | 2017-08-02 | The Regents of the University of California | Methods to produce ultra-thin metal nanowires for transparent conductors |
US10354773B2 (en) | 2016-04-08 | 2019-07-16 | Duke University | Noble metal-coated nanostructures and related methods |
EP3466570A4 (en) * | 2016-06-03 | 2020-01-22 | Bioneer Corporation | Method for manufacturing silver-coated copper nanowire having core-shell structure by using chemical reduction method |
US10566104B2 (en) | 2014-07-09 | 2020-02-18 | Daegu Gyeongbuk Institute Of Science And Technology | Metal nanowire having core-shell structure coated with graphene, and manufacturing method therefor |
CN111910165A (en) * | 2020-07-20 | 2020-11-10 | 上海空间电源研究所 | Exposed metal protection liquid and protection method in PECVD (plasma enhanced chemical vapor deposition) process |
CN111939927A (en) * | 2020-08-14 | 2020-11-17 | 西安建筑科技大学 | Copper-based catalyst with nanowire network structure and preparation method and application thereof |
US11413685B2 (en) | 2017-09-27 | 2022-08-16 | Dowa Electronics Materials Co., Ltd. | Silver powder mixture, method for producing same, and conductive paste |
CN115319081A (en) * | 2022-07-26 | 2022-11-11 | 天津科技大学 | Method for dispersing metal nanowires in organic solvents with different polarities |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5846598B2 (en) * | 2011-06-01 | 2016-01-20 | 国立大学法人大阪大学 | Synthesis method of nanoparticles |
CN104583114B (en) * | 2012-06-18 | 2017-04-05 | 苏州诺菲纳米科技有限公司 | The agglomerated thing of the nanowire suspended liquid being stored in container is reduced |
US9050775B2 (en) * | 2012-10-12 | 2015-06-09 | Nano And Advanced Materials Institute Limited | Methods of fabricating transparent and nanomaterial-based conductive film |
CN103212721B (en) * | 2013-05-10 | 2014-12-10 | 厦门大学 | Method for synthesizing copper nanowire under catalysis of nickel ions |
CN103498198B (en) * | 2013-10-24 | 2016-03-23 | 南京信息工程大学 | A kind of preparation method of positive pentagonal prism shape copper micro wire |
KR101516953B1 (en) * | 2013-11-20 | 2015-05-04 | 한국과학기술연구원 | Method for preparing copper nanowire, copper nanowire prepared by the same, ink composition, and method for preparing transparent conductive film |
WO2015097808A1 (en) * | 2013-12-26 | 2015-07-02 | 古河電気工業株式会社 | Method for producing copper nanowire, copper nanowire and use thereof |
CN103706785B (en) * | 2014-01-16 | 2017-02-01 | 中国科学院上海有机化学研究所 | Preparation method of copper nano material taking amino acid and analogs of amino acid as modifier |
CN103769607A (en) * | 2014-02-19 | 2014-05-07 | 四川大学 | Preparation method for nickel-copper nanowire |
CN103878384A (en) * | 2014-02-28 | 2014-06-25 | 江苏大学 | Core-shell structure Cu-based nanowire of composite Ni and Co and preparation method of core-shell structure Cu-based nanowire |
CN103911089B (en) * | 2014-04-21 | 2016-08-17 | 陈珍珍 | A kind of copper nano-wire conducting resinl and preparation method thereof |
KR20150145892A (en) * | 2014-06-19 | 2015-12-31 | (주)바이오니아 | Silver Coated Copper Nano Wire and Method for Manufacturing Thereof |
JP6581425B2 (en) * | 2014-08-19 | 2019-09-25 | 積水化学工業株式会社 | Transparent conductive film |
DE102015013219A1 (en) * | 2014-10-28 | 2016-04-28 | Dow Global Technologies Llc | Process for the preparation of silver nanowires |
KR102178777B1 (en) * | 2014-12-23 | 2020-11-13 | 솔브레인홀딩스 주식회사 | A composition for preparing copper nanowires and a method of manufacuring copper nanowires using the same |
CN104741618B (en) * | 2015-02-13 | 2016-10-05 | 燕山大学 | Utilize the method that bollworm polyhedrosis protein extract prepares Pt nanowires |
KR20160117905A (en) * | 2015-04-01 | 2016-10-11 | 한양대학교 산학협력단 | Composition for forming copper nanowire network by light sintering, method for preparing copper nanowire network, and transparent electrode including the same |
KR101719155B1 (en) | 2015-04-23 | 2017-04-04 | 한국과학기술연구원 | Metal nanowire, ink composition or transparent conductive film comprising the same, and the preparation method thereof |
CN104858450A (en) * | 2015-06-10 | 2015-08-26 | 苏州冷石纳米材料科技有限公司 | Method for preparing super-long copper nano-wires in batch |
KR20160146237A (en) | 2015-06-12 | 2016-12-21 | 전관구 | Metal mixture ink and manufacturing process for conductive thin film electrode |
WO2017004055A1 (en) | 2015-07-02 | 2017-01-05 | Sabic Global Technologies B.V. | Process and material for growth of adsorbed compound via nanoscale-controlled resistive heating and uses thereof |
CN105328204B (en) * | 2015-10-16 | 2017-10-13 | 苏州卫生职业技术学院 | A kind of preparation method of two-dimentional copper nanometer rods |
KR20170067204A (en) * | 2015-12-07 | 2017-06-16 | 삼성디스플레이 주식회사 | Manufacturing method of metal nanowire electrode |
CN105665743B (en) * | 2016-02-29 | 2017-08-25 | 吉林大学 | Copper nano-wire method is prepared under a kind of low temperature |
KR101842763B1 (en) * | 2016-03-11 | 2018-05-14 | 경희대학교 산학협력단 | preparation method of copper nano-structures |
JP6334076B2 (en) | 2016-03-14 | 2018-05-30 | ユニチカ株式会社 | Nanowire and manufacturing method thereof, nanowire dispersion and transparent conductive film |
WO2018084518A1 (en) * | 2016-11-02 | 2018-05-11 | (주)바이오니아 | Epoxy paste composition including silver-coated copper nanowires having core-shell structure, and conductive film including same |
CN107052358B (en) * | 2016-12-14 | 2020-03-31 | 中国科学技术大学 | Preparation method of copper nanowire |
KR102424876B1 (en) * | 2017-04-28 | 2022-07-22 | 엘지디스플레이 주식회사 | Encryption method using chiral metal nanostructure |
KR102429090B1 (en) | 2017-04-28 | 2022-08-03 | 엘지디스플레이 주식회사 | Metal nanostructures and method for manufacturing the same |
JP2019065375A (en) * | 2017-09-29 | 2019-04-25 | 株式会社原田伸銅所 | Copper alloy powder having antibacterial properties and antivirus properties and article using the same |
CN108393501B (en) * | 2018-04-13 | 2020-11-06 | 哈尔滨理工大学 | Preparation method of Cu nanowire with controllable diameter |
KR102197711B1 (en) * | 2018-10-31 | 2021-01-04 | (주)마잘 | Method for treating the surface of silver coated powder for electrically conductive paste |
CN109128144A (en) * | 2018-11-02 | 2019-01-04 | 南京工业大学 | Preparation method of copper nanocluster with wide response range to hydrogen peroxide |
US12064816B2 (en) * | 2018-11-20 | 2024-08-20 | Hunan Terry New Materials Co., Ltd. | Method for preparing metal powder by water atomization |
CN111715888B (en) * | 2019-03-20 | 2023-10-24 | 香港科技大学 | Copper-based nanostructure, method for producing the same, transparent conductive film, and electronic device |
CN110434353A (en) * | 2019-08-06 | 2019-11-12 | 徐少晨 | A kind of preparation method and applications of ball chain shape copper nano-wire |
CN110465653B (en) * | 2019-09-19 | 2021-11-05 | 安徽工业大学 | Silver wire and preparation method thereof |
CN110836920B (en) * | 2019-11-20 | 2021-07-02 | 山西大学 | Copper nanowire-molybdenum disulfide-graphene compound and preparation method and application thereof |
WO2021141109A1 (en) * | 2020-01-09 | 2021-07-15 | 国立大学法人北海道大学 | Super-water-repellent surface member, metal copper surface member, and method for manufacturing same |
KR102383772B1 (en) * | 2020-05-21 | 2022-04-07 | 한국과학기술원 | Transition metal chalcogenide for manufacturing metal nanostructures, metal nanostructures produced thereby, electronic devices including the same, and methods for manufacturing the same |
TWI793635B (en) * | 2020-06-15 | 2023-02-21 | 德克薩斯農工大學系統 | Copper nanowires and their use in plastics to improve thermal and electrical conductivity |
KR102302548B1 (en) * | 2020-06-29 | 2021-09-16 | 마이크로컴퍼지트 주식회사 | Preparing method of surface-treated metal nanowire |
CN111961421B (en) * | 2020-09-09 | 2021-10-15 | 深圳大学 | Water-based conductive adhesive and preparation method thereof |
WO2024070339A1 (en) * | 2022-09-30 | 2024-04-04 | 富士フイルム株式会社 | Conductive adhesive material-forming composition, conductive adhesive material, device, and method for producing conductive adhesive material |
KR20240120364A (en) * | 2023-01-31 | 2024-08-07 | 동아대학교 산학협력단 | Method for manufacturing high aspect ratio copper nanowires and copper nanowires accordingly |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3560333B2 (en) * | 2001-03-08 | 2004-09-02 | 独立行政法人 科学技術振興機構 | Metal nanowire and method for producing the same |
CN1322075C (en) * | 2002-06-13 | 2007-06-20 | 耐诺泡德斯工业有限公司 | A method for the production of conductive and transparent nano-coatings and nano-inks and nano-powder coatings and inks produced thereby |
US7566360B2 (en) * | 2002-06-13 | 2009-07-28 | Cima Nanotech Israel Ltd. | Nano-powder-based coating and ink compositions |
KR100486604B1 (en) * | 2002-10-30 | 2005-05-03 | (주)창성 | Method for manufacturing nano-scale copper powders by wet reducing process |
CN102250506B (en) * | 2005-08-12 | 2014-07-09 | 凯博瑞奥斯技术公司 | Nanowires-based transparent conductors |
CN100369703C (en) * | 2006-03-28 | 2008-02-20 | 华中师范大学 | Fe nanowire and preparation method thereof |
KR100790458B1 (en) * | 2006-07-10 | 2008-01-02 | 삼성전기주식회사 | Copper nano-particles and preparation method thereof |
KR100809982B1 (en) * | 2006-09-21 | 2008-03-06 | 삼성전기주식회사 | Method for manufacturing copper nanoparticles using microwave |
KR101545219B1 (en) * | 2006-10-12 | 2015-08-18 | 캄브리오스 테크놀로지즈 코포레이션 | Nanowire-based transparent conductors and applications thereof |
JP2010520626A (en) * | 2007-03-01 | 2010-06-10 | ピーケム アソシエイツ、インク. | Shielding with metallic nanoparticle compositions and related apparatus and methods |
JP5245112B2 (en) * | 2007-12-11 | 2013-07-24 | コニカミノルタ株式会社 | Transparent conductive film, transparent conductive film, and flexible transparent electrode |
WO2009107694A1 (en) * | 2008-02-27 | 2009-09-03 | 株式会社クラレ | Process for producing metal nanowire, and dispersion and transparent electroconductive film comprising the produced metal nanowire |
JP2011070820A (en) * | 2009-09-24 | 2011-04-07 | Panasonic Electric Works Co Ltd | Base material with transparent conductive film, and manufacturing method therefor |
-
2010
- 2010-12-07 SG SG10201408043RA patent/SG10201408043RA/en unknown
- 2010-12-07 CN CN2010800628951A patent/CN102792385A/en active Pending
- 2010-12-07 WO PCT/US2010/059236 patent/WO2011071885A2/en active Application Filing
- 2010-12-07 KR KR1020127017591A patent/KR20120115298A/en not_active Application Discontinuation
- 2010-12-07 EP EP10836521.4A patent/EP2510524A4/en not_active Withdrawn
- 2010-12-07 TW TW099142560A patent/TWI508922B/en not_active IP Right Cessation
- 2010-12-07 US US13/514,176 patent/US20130008690A1/en not_active Abandoned
- 2010-12-07 AU AU2010328361A patent/AU2010328361A1/en not_active Abandoned
- 2010-12-07 SG SG2012041968A patent/SG181565A1/en unknown
- 2010-12-07 JP JP2012543198A patent/JP2013513220A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of EP2510524A4 * |
Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013019020A2 (en) * | 2011-07-29 | 2013-02-07 | Lg Innotek Co., Ltd. | Nano-wire and method for manufacturing the same |
WO2013019020A3 (en) * | 2011-07-29 | 2013-04-25 | Lg Innotek Co., Ltd. | Nano-wire and method for manufacturing the same |
US9956616B2 (en) | 2011-07-29 | 2018-05-01 | Lg Innotek Co., Ltd. | Nano-wire and method for manufacturing the same |
KR101334601B1 (en) * | 2011-10-11 | 2013-11-29 | 한국과학기술연구원 | Metal nanowire with high linearity, fabrication method of the same and transparent conducting film comprising the same |
US20140299821A1 (en) * | 2011-11-03 | 2014-10-09 | Bayer Intellectual Property Gmbh | Method for producing a metal nanoparticle dispersion, metal nanoparticle dispersion, and use of said metal nanoparticle dispersion |
WO2013086139A1 (en) * | 2011-12-07 | 2013-06-13 | Duke University | Synthesis of cupronickel nanowires and their application in transparent conducting films |
CN104040641A (en) * | 2011-12-07 | 2014-09-10 | 杜克大学 | Synthesis of cupronickel nanowires and their application in transparent conducting films |
US9993875B2 (en) | 2012-01-30 | 2018-06-12 | Nthdegree Technologies Worldwide, Inc. | Methods for fabrication of nanostructures |
JP2013159809A (en) * | 2012-02-03 | 2013-08-19 | Unitika Ltd | Method for producing copper fine particle, copper fine particle obtained by the method, and coating material using the copper fine particle |
CN102601382A (en) * | 2012-03-27 | 2012-07-25 | 苏州冷石纳米材料科技有限公司 | Method for massively preparing overlength copper nanowires |
WO2013187384A1 (en) * | 2012-06-11 | 2013-12-19 | ユニチカ株式会社 | Fibrous copper microparticles and method for manufacturing same |
JPWO2013187384A1 (en) * | 2012-06-11 | 2016-02-04 | ユニチカ株式会社 | Fibrous copper fine particles and method for producing the same |
WO2014004712A1 (en) * | 2012-06-28 | 2014-01-03 | Nthdegree Technologies Worldwide Inc. | Systems and methods for fabrication of nanostructures |
JP2014037602A (en) * | 2012-08-20 | 2014-02-27 | Furukawa Electric Co Ltd:The | Method for producing copper nanowire, copper nanowire and application thereof |
WO2014063769A1 (en) * | 2012-10-25 | 2014-05-01 | Merck Patent Gmbh | Processing of copper-based nanowires for transparent conductors |
JP2014133946A (en) * | 2012-12-14 | 2014-07-24 | Unitika Ltd | Aggregate of fibrous copper fine particle, manufacturing method of aggregate of fibrous copper fine particle |
JP2014118589A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Coated fibrous copper fine particle aggregate |
JP2014118590A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Fibrous silver fine particle aggregate |
WO2015120960A1 (en) * | 2014-02-11 | 2015-08-20 | Merck Patent Gmbh | Green chemistry method of making copper nanowires |
US10566104B2 (en) | 2014-07-09 | 2020-02-18 | Daegu Gyeongbuk Institute Of Science And Technology | Metal nanowire having core-shell structure coated with graphene, and manufacturing method therefor |
EP3197901A1 (en) * | 2014-09-26 | 2017-08-02 | The Regents of the University of California | Methods to produce ultra-thin metal nanowires for transparent conductors |
CN104475755A (en) * | 2014-12-30 | 2015-04-01 | 山西森达源科技有限公司 | Preparation method of spheroidal ultrafine silver powder for front surface of solar cell |
WO2016122412A1 (en) | 2015-01-30 | 2016-08-04 | Nanyang Technological University | Conductive paste, method for forming an interconnection and electrical device |
EP3251129A4 (en) * | 2015-01-30 | 2018-08-29 | Nanyang Technological University | Conductive paste, method for forming an interconnection and electrical device |
US10202512B2 (en) | 2015-01-30 | 2019-02-12 | Nanyang Technologies University | Conductive paste, method for forming an interconnection and electrical device |
US10354773B2 (en) | 2016-04-08 | 2019-07-16 | Duke University | Noble metal-coated nanostructures and related methods |
EP3466570A4 (en) * | 2016-06-03 | 2020-01-22 | Bioneer Corporation | Method for manufacturing silver-coated copper nanowire having core-shell structure by using chemical reduction method |
US11413685B2 (en) | 2017-09-27 | 2022-08-16 | Dowa Electronics Materials Co., Ltd. | Silver powder mixture, method for producing same, and conductive paste |
CN111910165A (en) * | 2020-07-20 | 2020-11-10 | 上海空间电源研究所 | Exposed metal protection liquid and protection method in PECVD (plasma enhanced chemical vapor deposition) process |
CN111939927A (en) * | 2020-08-14 | 2020-11-17 | 西安建筑科技大学 | Copper-based catalyst with nanowire network structure and preparation method and application thereof |
CN111939927B (en) * | 2020-08-14 | 2022-11-04 | 西安建筑科技大学 | Copper-based catalyst with nanowire network structure and preparation method and application thereof |
CN115319081A (en) * | 2022-07-26 | 2022-11-11 | 天津科技大学 | Method for dispersing metal nanowires in organic solvents with different polarities |
CN115319081B (en) * | 2022-07-26 | 2024-05-24 | 天津科技大学 | Method for dispersing metal nanowires in organic solvents with different polarities |
Also Published As
Publication number | Publication date |
---|---|
TW201130740A (en) | 2011-09-16 |
CN102792385A (en) | 2012-11-21 |
KR20120115298A (en) | 2012-10-17 |
WO2011071885A3 (en) | 2011-10-13 |
JP2013513220A (en) | 2013-04-18 |
TWI508922B (en) | 2015-11-21 |
SG10201408043RA (en) | 2015-01-29 |
EP2510524A2 (en) | 2012-10-17 |
AU2010328361A1 (en) | 2012-07-26 |
US20130008690A1 (en) | 2013-01-10 |
EP2510524A4 (en) | 2014-10-01 |
SG181565A1 (en) | 2012-07-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20130008690A1 (en) | Compositions and methods for growing copper nanowires | |
US9972742B2 (en) | Method for forming a transparent conductive film with metal nanowires having high linearity | |
EP3466570B1 (en) | Method for manufacturing silver-coated copper nanowire having core-shell structure by using chemical reduction method | |
EP3159078B1 (en) | Method of preparing a silver-coated copper nanowire | |
US8512438B2 (en) | Methods for controlling metal nanostructures morphology | |
KR101474040B1 (en) | Dispersion solution of metal nanoparticle, method for production thereof, and method for synthesis of metal nanoparticle | |
Yang et al. | One-pot rapid synthesis of high aspect ratio silver nanowires for transparent conductive electrodes | |
CN102251278B (en) | Controllable preparation method of monocrystal copper nanowires | |
US20180247722A1 (en) | Transparent conductors | |
US20140342177A1 (en) | Synthesis of cupronickel nanowires and their application in transparent conducting films | |
Park et al. | Fabrication of dendritic silver-coated copper powders by galvanic displacement reaction and their thermal stability against oxidation | |
CA2692067C (en) | Organoamine stabilized silver nanoparticles and process for producing same | |
JP2013502515A (en) | Purification of metal nanostructures to improve haze in transparent conductors made from metal nanostructures | |
Lau et al. | Silver nanowires as flexible transparent electrode: Role of PVP chain length | |
JP2008013846A (en) | Method for producing metal nanoparticle, and metal nanoparticle | |
CN105014091B (en) | A kind of overlength corronil nano wire and preparation method thereof | |
Mao et al. | Large-scale synthesis of AgNWs with ultra-high aspect ratio above 4000 and their application in conductive thin film | |
JP2009062611A (en) | Metal fine particle material, dispersion liquid of metal fine particle material, conductive ink containing the dispersion liquid, and their manufacturing methods | |
Zhao et al. | An eco-friendly nitrate-free method for the synthesis of silver nanowires with reduced diameters | |
Jiang et al. | A rapid green route for fabricating efficient SERS substrates | |
Silva et al. | Cyclodextrin inclusion compound crystals for growth of Cu–Au core–shell nanoparticles | |
Feng et al. | Production of Ag nanowires with high yield and narrow size distribution by promoting nucleation through hot injection and their application to disposable paper electrodes | |
Tomioka et al. | Lowered melting point of polyvinyl pyrrolidone bound 1D silver nanowires |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080062895.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10836521 Country of ref document: EP Kind code of ref document: A1 |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10836521 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012543198 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010328361 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010836521 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20127017591 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1657/KOLNP/2012 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 2010328361 Country of ref document: AU Date of ref document: 20101207 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13514176 Country of ref document: US |