WO2012011774A2 - 은 나노와이어의 제조방법 - Google Patents

은 나노와이어의 제조방법 Download PDF

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WO2012011774A2
WO2012011774A2 PCT/KR2011/005426 KR2011005426W WO2012011774A2 WO 2012011774 A2 WO2012011774 A2 WO 2012011774A2 KR 2011005426 W KR2011005426 W KR 2011005426W WO 2012011774 A2 WO2012011774 A2 WO 2012011774A2
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solution
silver
nanowires
silver nanowires
manufacturing
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PCT/KR2011/005426
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English (en)
French (fr)
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WO2012011774A9 (ko
WO2012011774A3 (ko
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김상호
문석식
배창완
서동민
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공주대학교산학협력단
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Priority to US13/811,342 priority Critical patent/US9636746B2/en
Priority to CN201180045971.2A priority patent/CN103153844B/zh
Priority claimed from KR1020110072756A external-priority patent/KR101307967B1/ko
Priority claimed from KR1020110072762A external-priority patent/KR101307973B1/ko
Publication of WO2012011774A2 publication Critical patent/WO2012011774A2/ko
Publication of WO2012011774A9 publication Critical patent/WO2012011774A9/ko
Publication of WO2012011774A3 publication Critical patent/WO2012011774A3/ko

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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a manufacturing method of silver nanowires, and more specifically, to a method of mass production of silver nanowires in a very short time by using liquid chemistry, which is uniform in size and longer than lOjtmi. It is about mass production of silver, and most of the injected silver precursors are made of silver nanowires with very high efficiency.
  • Electric conductivity is high, so the utilization value is high in electricity, magnetism, optical element and sensor.
  • silver (Ag) has the best electrical and thermal conductivity of all metals, and its optical properties are excellent, with its highest surface enhancement in the visible range.
  • the most important technique is to mass produce nanowires in relaxed conditions.
  • silver nanowires have a very high utilization value as electric, magnetic, optical elements, and sensors.
  • silver nanowire synthesis method using a liquid chemistry method commonly used as in US Patent Publication No. 2007-0034052 is a nanowire. It is difficult to control the size and shape of the fabric, the size deviation of the manufactured nanowires is very severe, the reaction time is long, and the mass production is extremely difficult.
  • the object of the present invention is to provide a method for producing silver nanowires with a very high efficiency in a very short time by using a liquid phase chemical method of atmospheric pressure low temperature, the diameter is very uniform, and the diameter deviation of the nanowires manufactured It provides a method of manufacturing nanowires that are small, have a length of more than 5 / m, and have a high long-term reduction ratio, and effectively suppress the amount of silver precursors that are unreacted to produce nanowires with high efficiency.
  • a method for producing silver nanowires includes a silver salt; a water-soluble polymer; a surfactant or a metal catalyst which is a halide of a metal ion having a standard reduction potential of -0.1 to -0.9 V; and a reducing solvent; Ag) Nanowires have the characteristic of manufacturing.
  • the reducing solvent is a polar solvent containing at least one oxygen atom.
  • the reducing solvent is ethylene glycol (Ethylene Glycol),
  • the surfactant can be used to produce a large amount of nanowires in a very short time even during scale-up, and the amount of silver salts introduced is converted to silver nanowires of 90 mol% or more, and the high concentration of the silver precursor There is an advantage to the production of silver nanowires of uniform size from solution.
  • the manufacturing method of the present invention has the feature that, by using the metal catalyst, the percentage of increase in silver nanowires is 95% by weight or more, and more specifically 99% by weight, in the total amount of silver product synthesized.
  • the surfactant has at least one selected feature from anionic surfactants, cationic surfactants and amphoteric surfactants.
  • the anionic surfactant is a hydrophilic moiety is a carboxylate, sulfate salt, sulfonate salt, or a mixture thereof,
  • the anionic surfactant is represented by the following Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3.
  • R is independently an alkyl group of 10 to 20 carbon atoms or an alkenyl group of 10 to 20 carbon atoms
  • n is an integer of 1 to 5
  • R 2 is an alkyl group of 12 to 20 carbon atoms, 12-20 alkenyl group or C12-20 alkylaryl group.
  • the cationic surfactant is an amine salt, a quaternary ammonium salt, an onium compound, or a mixture thereof, in which the hydrophilic portion contains primary to tertiary amines.
  • the quaternary ammonium salt is a nitrogen-containing compound containing chain alkyl.
  • nitrogen-containing cyclic nitrogen compounds include cyclic nitrogen compounds.
  • the onium compound includes a phosphonium, sulfonium salt or a mixture thereof, and the nitrogen heterocyclic compound includes a pyridium salt, quinolium, imidazolium or a mixture thereof.
  • the cationic surfactant is a quaternary containing ester
  • Ester-containing quaternary ammonium salts (EQ), amide group and ester group in Quaternary Ammonium salts, pyridinium derivatives, betaine derivatives, imidazolium derivatives , Quinolinium derivatives, piperazinium
  • the surfactant may be a commercially available material.
  • the surfactant may be a commercially available material. For example,
  • ASCO ® Kay Chemtech's LDBAC (ASCO ® ), IMQ (ASCO ® ), EQ (ASCO ® ), EAQ (ASCO ® ), CTAC (ASCO «), 24-3 / 28 (ASCO ® ), 1416 (ASCO Commercially available surfactants such as ® ), BT (ASCO ® ) or ZW (ASCO ® ).
  • the anionic surfactant is sodium laureth.
  • the cationic surfactant is at least one selected from Formula 4, Formula 5, Formula 6, Formula 7, Formula 8, Formula 9, and Formula 10 below.
  • R 3 , R 4 , R 6 and R 10 are each independently an alkyl group having 1 to 5 carbon atoms, and R 5 , R 7 , R 8 , R 9, and R 13 are each independently carbon 10; It is an alkyl group of ⁇ 20 or an alkenyl group of 10 to 20 carbon atoms, wherein Ru is an alkyl group of 12-20 carbon atoms or of 12-20 carbon atoms And alkenyl groups, wherein R is an alkyl group having 1 l2 eu 3, wherein p and q are each other
  • W, W 2 , W 3, and W 4 are each independently 0, S, or NH, and the above?,-,? 2- ,? 3 %? 4- ,? 5 And 6 6 are independently of each other C1- or CH: oso 3 ).
  • amphoteric surfactant may be at least one of Formula 11 and Formula 12 below.
  • R 4 and R J7 are independently of each other an alkyl group or a carbon number of 12-20 carbon atoms.
  • R 12 to 20 alkenyl group wherein R, 5 is COO-, P0 3 H- or S0 3- , R 16 is hydrogen or an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 1 to 10 carbon atoms, R 18 is OCOO-, OP0 3 H, OS0 3 -or S0 3- , wherein r, s and t are integers of 1 to 5 independently of each other, and Xf and X 8 -are independently of each other C1- or CH 3 OS0 3 ⁇ , wherein Y, + and ⁇ 2 + are independently of each other Na + , K + or Li + .)
  • the surfactant has the greatest effect on the reaction time during the synthesis of the silver nanowire, and furthermore, the shape of the silver product produced by the reaction and the size (diameter and length) of the silver nanowire. This affects the variation, the possibility of mass production by scale-up, and the reaction efficiency in nanowire synthesis.
  • the surfactant according to the present invention it is possible to produce nanowire-like silver in a very short time (less than 30 minutes) even in mass production, and to increase the yield of silver nanowire synthesis, There is a feature to evenly control the size of multiple silver nanowires produced simultaneously by a synthesis.
  • At least 90% (mol%) of silver (Ag) in the form has a very high conversion efficiency, which is made of silver nanowires, and the synthesis required for the production of silver nanowires by adopting a surfactant according to the present invention. Surprisingly It has the effect of being shortened, and in the case of mass production by scale-up, a large amount of silver nanowires are manufactured in a very short time within 30 minutes.
  • the weight ratio of the silver salt: surfactant is preferably 100: 0.01 to 15, and 100:
  • 1 to 15 is more preferable than 100 silver salts.
  • the amount of the surfactant is less than 0.001 part by weight, it is difficult to obtain the effect by the addition of the above-described surfactant, and if it exceeds 1 part by weight, there is a risk of not synthesizing the nanowires, which may adversely affect pollution.
  • the precursor solution contains a halide of silver with a metal having a standard reduction potential of -0.1 to -0.9 V
  • other than nanowires can not only prevent the synthesis of silver products. It is characterized by the fact that nanowires with an aspect ratio of 100 or more are manufactured.
  • the standard reduction potential of the metal ion of the metal catalyst which is the metal halide
  • the metal ion of the metal catalyst which is the metal halide
  • the metal silver is Ni 2+ (standard reduction potential -0.25 V).
  • the metal catalyst is Ni 2+ . It is characterized by the fact that it is a halide of at least one selected ion from Co 2+ , Cr 3+ and Zn 2+ , the halide comprising chloride, bromide, flutuoride, iodide or a combination thereof. In order to further enhance the synthesis rate to nanowires in time, the halide is preferably a chloride.
  • the weight ratio of the silver salt: metal catalyst is 100: 0.01 to 1, and preferably, the increase ratio of the silver salt; metal catalyst is 100: 0.01 to 0.2.
  • the weight ratio of the silver salt to the metal catalyst is to prevent the formation of silver nanoparticles, silver nanoplates and silver nanorods in the silver product produced by the reaction regardless of the scale of the reaction of the silver nanowires. Ratio.
  • the water-soluble polymer is attached to the side when the silver nanowires are manufactured.
  • the average length is 30 ⁇ to 70 by controlling the molecular weight (Mw) of the water-soluble polymer from 50,000 to 1,500,000; Phosphorus has the feature of manufacturing nanowires.
  • the water-soluble polymer is one or more selected from polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid and copolymers thereof. Preferred, and polyvinylpyrrolidone.
  • the manufacturing method of the present invention in combination with the surfactant or metal catalyst described above, controls the stirring conditions and the viscosity of the precursor solution during heating of the precursor solution, thereby controlling the length and shortening ratio of the produced silver nanowires. There is this.
  • the manufacturing method of the present invention controls the stirring conditions when heating the precursor solution, thereby improving the long axis length (hereinafter, the length) of the silver nanowires.
  • the viscosity of the precursor solution is controlled to reduce the shortening length (hereinafter diameter) of the silver nanowires.
  • the precursor solution is characterized in that the precursor solution is in an unstirred state or satisfies Equation 1 below when heating the precursor solution.
  • V is the average flow rate of the precursor solution.
  • the non-stirring state means that no artificial stirring is performed, and that no change in flow rate or turbulence occurs by an external device, but includes natural convection in the solution.
  • the manufacturing method according to the present invention is characterized by controlling the long axis length of the silver nanowires manufactured by controlling the stirring state of the precursor solution to satisfy the unstirred or relation 1, more than 10; There is a feature of producing uniformly sized silver nanowires with lengths greater than m .
  • the precursor solution further includes a thickener, and a silver nanowire whose diameter is controlled by the thickener is manufactured.
  • the thickener content of the precursor solution is determined by the thickener and the reducing property.
  • the solvent mixture has a viscosity of 1.1 to 10 times based on the viscosity of the reducing solvent, and a very small nucleus is generated in the thickener and lateral growth perpendicular to the longitudinal direction is suppressed.
  • silver nanowires having a shorter length of 50 nm or less and practically 20 to 50 nm are manufactured.
  • the thickener is preferably polyethylene glycol, and the polyethylene glycol may have a molecular weight of 200 to 20000.
  • the surfactant can produce silver nanowires of even size with a high conversion efficiency in a very short time.
  • the long axis length of the nanowires can be controlled by the stirring state of the precursor solution, and the diameter of the silver wires can be controlled by the thickener.
  • the surfactant can produce silver nanowires of even size with a high conversion efficiency in a very short time, and the silver metal nanorods other than silver nanowires by the metal catalyst. , Prevent unwanted formations such as silver nanoparticles and silver nanoplates, and can manufacture silver nanowires with aspect ratios of 100 or more.
  • the long axis length of silver nanowires can be controlled by the stirring state of the precursor solution.
  • the diameter of the wire can be controlled.
  • the surfactant may produce nanowires having an average diameter of 60 to 90 nm and an average length of 5 to 9 / m.
  • the average diameter is controlled by controlling the stirring state of the surfactant and the precursor solution. 40 to 70 nm, the average length is more than 10 ⁇ , more specifically 20 to 100 phosphorus can manufacture nanowires,
  • surfactants can produce nanowires with an average diameter of 20 to 50 nm, an average length of at least 10 i and more characteristic 20 to 50 zm.
  • the metal catalyst has an average diameter of 60 to 80 nm, an average length of 5 / m or more, and more specifically, 8 to 20 ⁇ , which is capable of manufacturing nanowires, and stirring the metal catalyst and the precursor solution.
  • the average length of 20 or more, more specifically 20 to 50 jtrni, and the average diameter of 70 to 100 nm can be produced nanowires, the average diameter by the stirring state and thickener of the metal catalyst, precursor solution.
  • the average length is more than 20, more specifically 20 / im to 60; zm is possible to manufacture a nanowire, the stirring state of the metal catalyst, precursor solution and
  • the average length of 30 or more, more specifically, 30 urn to 70 jMn, the average diameter of 80 to llOnm has a feature that can be produced nanowires.
  • a method for producing silver nanowires includes: a) a first solution containing an silver salt and a first reducing solvent, a surfactant or a metal catalyst, a water-soluble polymer, a thickener, and a second reducing agent. Preparing a second solution containing a solvent; b) heating the second solution; and c) injecting the first solution into the second solution to produce silver (Ag) nanowires. Thereafter, d) recovering the silver nanowires manufactured using solid-liquid separation may be further performed.
  • the manufacturing method according to the present invention adopts the above-described surfactant or metal catalyst and at the same time uses silver salt as a silver precursor for producing silver nanowires, and a silver precursor and a surfactant or a silver precursor and a metal catalyst.
  • the present invention has a feature of producing silver nanowires by selectively heating a solution dissolved in a surfactant or a metal catalyst and mixing a mixture of a surfactant or a metal catalyst dissolved in a solution and a silver precursor solution.
  • the heating temperature of the second solution performed in step b) satisfies relation 2 below.
  • the Th is the heating temperature of the second solution ( 0 C), and the Tb is the atmospheric boiling point (° C) of the low alcohol (low alcohol of the second solution))
  • the heating temperature of the relation 2 is the nucleation and growth driving force of the silver nanowires.
  • the thickener is preferably contained in the second solution, and the thickener contained in the second solution has a viscosity of 1.1 to 10 times based on the viscosity of the second reducing solvent of the second solution. It is desirable that the amount to be.
  • the temperature change of the second solution upon the mixing of the second solution and the first solution affects the quality and shape of the silver nanowires to be manufactured.
  • step c) by the heating of the step b)
  • the temperature of the second solution is maintained. That is, it is preferable to prepare silver (Ag) nanowires by maintaining the heated state of the second solution and injecting the first solution into the second solution.
  • the temperature change of the second solution during the addition of the first solution satisfies the following Equation 3, and more preferably satisfies Equation 3-1.
  • the number of stitches 2 is the absolute value of the temperature (T t ) of the second solution at a specific time during the introduction of the second solution minus the temperature ( ⁇ 2 ) by the heating in step b). Means. According to a feature of the present invention, after the addition of the first solution is completed, the reaction is completed within 30 minutes, and the temperature by heating in step b) during the reaction time after the addition of the first solution is performed. Of course, it is maintained to satisfy.
  • the first solution is preferably discontinuously introduced into the second solution, in detail, the c In the step), the first solution is preferably added dropwise to the second solution at 0.01 to 5% by volume based on the volume (VI) of the first solution.
  • the stirring state in step c) also affects the shape of the nanowire to be manufactured, and is more preferable than the relational formula 3 above, independently of the stirring state. It is preferable that relation 3-1 is satisfied.
  • the second solution in the step c), during the introduction and reaction time of the first solution, the second solution has a feature that satisfies an unstirred state or relation 1-1.
  • V 2 is the average flow rate of the second solution.
  • the length of the long axis of the silver nanowires manufactured by controlling the stirring state of the second solution during the reaction period of the first solution and the reaction time after the injection may be controlled, and the uniform size may be controlled. It has the feature of manufacturing nanowires having.
  • step c) the second solution is in an unstirred state or a state satisfying relation 1-1.
  • the average diameter of 40 to 70 nm, the average length of more than 10 jtrni, more specifically 20 to 100 / II1 of the nanowire can be produced
  • the flow rate is the average flow rate of the fluid that is the second solution in step c)
  • the unstirred state means that no artificial agitation is performed, and that no change in flow rate or turbulence is caused by an external device, but includes natural convection in a solution.
  • silver salt water-soluble polymer, surfactant, thickener and reducing solvent
  • the reducing solvent is a polar solvent containing at least one oxygen atom.
  • the reducing solvent may be ethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,2-propylene glycol, diethylene glycol.
  • DEG Diethylene Glycol
  • At least one of glycerol and glucose is selected. This is to control nanowire diameter, length control and reaction speed control through reduction force control.
  • the first reducing solvent that dissolves silver salts is ethylene glycol (Ethylene). Glycol), 1,2-propylene glycol, 1,3-propylene
  • Glycol (2-Hydroxyethyl Ether), glycerol and glucose, surfactants and water-soluble polymers, preferably
  • At least one of glycerol and glucose is selected.
  • the first reducing solvent and the second reducing solvent are preferably the same substance.
  • the reducing solvent and the second reducing solvent are ethylene glycol.
  • the silver salt may be used as long as it is a silver salt dissolved in a reducing solvent.
  • One or more selected from silver nitrate, silver acetate, silver perchlorate and silver chloride One or more selected from silver nitrate, silver acetate, silver perchlorate and silver chloride.
  • the water-soluble polymer is attached to the side when the silver nanowires are manufactured.
  • the molecular weight of the water-soluble polymer (Mw) is preferably between 50,000 and 1,500,000.
  • the first solution which is a solution in which the silver precursor is dissolved, has a feature of containing 15 to 40% by weight of silver salt, and according to the present invention, By using the first solution containing the precursor material (silver precursor), it is possible to manufacture silver nanowires with high efficiency in a very fast time, wherein the second solution contains 1 to 15% by weight of water-soluble polymer. There is a feature that contains 0.005 to 1% by weight of surfactant.
  • the first solution and the second solution are silver salts:
  • the increase ratio is mixed at a ratio of 100: 0.01 to 15, wherein the thickener in the second solution is contained in the first reducing solvent of the volume contained in the first solution and the second reducing property of the volume contained in the second solution.
  • the mixed solvent Based on the viscosity of the mixed solvent in which the solvent is mixed (based on 25 ° C), the mixed solvent has an amount of 1.1 to 10 times the viscosity (based on 25 ° C).
  • the silver salt content of the first solution which is a solution in which the silver precursor is dissolved, is 1 to 12 weight ⁇ 3 ⁇ 4, wherein the second solution
  • the water-soluble polymer content is 0.5 to 12 wt%, and the content of the metal catalyst is 0.0001 to 0.02 wt%.
  • the first solution and the second solution are silver salts: a metal catalyst.
  • the weight ratio is 100: 0.01 to 1
  • the thickener contained in the second solution is the second reducing property of the volume of the first reducing solvent and the volume of the second solution contained in the first solution.
  • the mixed solvent Based on viscosity (25 0 C standard), the mixed solvent has a viscosity of 1.1 to 10 times (25 ° C. standard).
  • the present invention provides a transparent electrode containing silver nanowires manufactured by the above-described manufacturing method.
  • the transparent electrode includes a front electrode of a solar cell.
  • the silver nanowires manufactured according to the present invention have a high aspect ratio, As the thickness is controlled and uniformly sized, the transparent electrode of the present invention has extremely good and uniform electrical conductivity by mixing and applying silver nanowires, and maintains excellent electrical conductivity even with a small amount of silver nanowires. In addition, it has a feature of being a transparent electrode having excellent light transmittance.
  • the manufacturing method according to the present invention is characterized by a dramatic increase in the amount of silver nanowires produced by a simple scale-up without technical change in the degree of synthesis of silver nanowires. It has been designed to produce large quantities of silver nanowires in a very short time within 30 minutes, even in mass production by scale-up, and to produce nanowires of uniform length with standard deviations within 30% of the average length. It is characterized by the ability to independently control the length and diameter of silver nanowires, and more than 90 mol% of silver salts introduced during the reaction are made of silver nanowires. Silver nanorods, silver nanoparticles and silver nanoplates other than nanowires It is possible to prevent the formation of unwanted products such as, having a uniform size and an average aspect ratio of 100 or more
  • FIG. 1 is a scanning electron micrograph of the silver nanowires prepared in Example 1
  • FIG. 2 is a scanning electron micrograph of the silver nanowires prepared in Example 2
  • FIG. 4 is a scanning electron microscope picture of the silver nanowires prepared in Example 3
  • FIG. 5 is a scanning electron microscope picture of the silver nanowires prepared in Example 4
  • FIG. Silver-scanned electron micrographs of nanowires prepared in 5 7 is a scanning electron micrograph of the silver nanowires prepared in Example 6, and
  • FIG. 8 is a high magnification scanning electron microscope of the silver nanowires prepared in Example 6.
  • FIG. 9 is a scanning electron micrograph of the silver nanowires prepared in Example 7
  • FIG. 10 is a scanning electron micrograph of the silver nanowires prepared in Example 8
  • FIG. Scanning electron micrograph of the silver nanowires prepared in Example 9 Figure 12 is a scanning electron micrograph of the silver nanowires prepared in Example 10
  • Figure 13 is a scanning electron micrograph of the silver nanowires prepared in Example 11 14 shows a high magnification scanning electron microscope of silver nanowires prepared in Example 11.
  • Wabetaine Cocoamidopropyl Bentaine, AK Chemtech, CAS registry
  • the second solution was added to a 50 ml isometric bottom flask, the second solution was heated to 160 ° C using an oil bath, the second solution was stirred at 250 rpm, and the heated second was heated.
  • the first solution was added dropwise at a rate of 0.02 m sec to the solution by using a micropipette. At this time, it was confirmed that the temperature change of the second solution was maintained within ⁇ 3 ° C.
  • the reaction was confirmed to turn milky white and cooled to room temperature to complete the reaction.
  • the silver nanowires were sedimented, the solvent layer was discarded, the solvent layer was discarded, and then the silver nanowires were recovered by repeating the process of centrifugation and discarding the solvent, followed by centrifugation and discarding the solvent.
  • the second solution was introduced into a 2 L reaction vessel having a diameter of 20 cm, and the second solution was heated to 160 ° C using an oil bath, and the second solution was stirred at 250 rpm.
  • the first solution was added dropwise to the second solution at a rate of 0.08 mL / sec using micro pipetteol. At this time, it was confirmed that the change in the silver content of the second solution was maintained within ⁇ 5 0 C.
  • the reaction was confirmed to turn milkywhite and cooled to room temperature to complete the reaction.
  • the second solution was added to a 50 ml isometric bottom flask, and the second solution was heated to 160 ° C using an oil bath, and the second solution was stirred at 250 rpm.
  • the first solution was added dropwise to the low 12 solution at a rate of 0.02 mL / sec using a micropipette. At this time, it was confirmed that the temperature change of the second solution was maintained within ⁇ 3 ° C.
  • reaction was confirmed to turn milkywhite and the phase was cooled to finish reaction.
  • the second solution was introduced into a 2 L reaction vessel having a diameter of 20 cm, and the second solution was heated to 150 ° C. using an oil bath, and the second solution was stirred at 250 rpm. Using micro pipetteol in the second solution, drop the first solution at a08m! Jsec. At this time, it was confirmed that the temperature change of the second solution was maintained within ⁇ 5 ° C when the first solution was dropped.
  • the reaction was confirmed to turn milkywhite and cooled to room temperature to complete the reaction.
  • Example 1 The first solution of Example 1 was heated to 160 ° C., and the first solution was added dropwise at a rate of 0.02 mL / sec using a micropipette to the heated second solution without stirring the second solution. Except for this, nanowires were prepared in the same manner as in Example 1.
  • Nanowires were prepared in the same manner as in Example 1 except that the first solution was added dropwise at a rate of 0.02 mL / sec using a pipette.
  • the viscosity at 25 ° C. of the solvent in which 4.5 mL of ethylene glycol and 0.5 mL of polyethylene glycol was mixed was 20 cp.
  • Ethylene glycol and 75 mL of polyethylene glycol (PEG, Mw 55,000) were used, and the prepared second solution was heated to 160 ° C., the second solution was stirred at 30 rpm, and the micropipette was used in the heated low 12 solution.
  • a nanowire was prepared in the same manner as in Example 2, except that the first solution was added dropwise at a rate of 0.08 mL / sec. 675 mL of ethylene glycol and 75 mL of polyethylene glycol were mixed.
  • the viscosity at 25 ° C. was 20 cps.
  • Viscosity 16.1cp
  • a second solution was added to a 50 ml isometric bottom flask having a diameter of 0.5 cm, the second solution was heated to 160 ° C using an oil bath, and the second solution was stirred at 800 rpm.
  • the first solution was added dropwise at a rate of 05 mL / sec to the heated second solution using a micropipette. At this time, the temperature change of the second solution was decreased.
  • the silver nanowires were sedimented and the solvent layer was discarded, then the distillate layer was added, and then the silver nanowires were re-dispersed, followed by the centrifugation and the discarding of the solvent twice.
  • Example 8 except that the first solution was added without stirring the second solution, and the addition and reaction of the first solution were completed without stirring, nanowires were prepared in the same manner as in Example 8. .
  • Silver nanowires were prepared in the same manner as in Example 9 except that PVP (Mw 1,000,000) was used instead of PVP (Mw 55,000).
  • the viscosity at 25 ° C was 40 cps, and the viscosity at 25 ° C for a solvent containing 20 mL of ethylene glycol and 5 mL of polyethylene glycol was 30 cps.
  • the second solution was heated to 160 o C using an oil bath, and the second solution was heated.
  • the first solution was added dropwise at a rate of 0.05 mL / sec using a micropipette to a heated second solution stirred at 800 rpm, indicating that the temperature change of the second solution was maintained within ⁇ 3 ° C. Confirmed.
  • the nanowires were recovered.
  • Example 1 is a scanning electron microscope for observing the silver nanowires prepared in Example 1
  • Nanowires were fabricated. Scanning electron microscopes show that the average diameter is 70 nm and the average length is 7 mi. The silver nanowire has a length deviation of 8.77 and a deviation within 70.76% of the average length. It was confirmed that uniformly sized silver nanowires were prepared. Also, 94% of the silver salts introduced into the reaction were converted into silver nanowires.
  • FIG. 2 is a scanning electron micrograph of the silver nanowire manufactured in Example 2, and has a uniform size similar to that of Example 1 by scale-up.
  • nanowires are manufactured, which can be produced in a short time of less than 30 minutes, and in very short time of less than 10 minutes based on the examples; With a length of ⁇
  • nanowires are mass produced.
  • FIG. 3 (a) is a scanning electron micrograph of the silver nanowire manufactured in Example 1
  • FIG. 3 (b) is an energy dispersive spectroscopy (EDS) measured in regions 1 to 4 of FIG. 3 (a). Similar EDS results were obtained in all areas of all manufactured nanowires, and only (Ag) was detected except for the material (Cu) which was added secondary for analysis, such as coating materials.
  • EDS energy dispersive spectroscopy
  • Figure 4 is a scanning electron microscope for observing the silver nanowires prepared in Example 3.
  • Example 5 is a scanning electron micrograph of the silver nanowires prepared in Example 4. Even when anionic surfactants were used, similar results to the cationic surfactants were obtained, and high efficiency was achieved in a short time by simple scale-up. It can be seen that the nanowires are mass produced.
  • Example 6 is a scanning electron microscope for observing the silver nanowires prepared in Example 5.
  • nanowires were manufactured by manufacturing nanowires in an unstirred state with an average diameter of 50 nm and an average length of 80 microns.
  • FIG. 7 and 8 are scanning electron micrographs of the silver nanowires prepared in Example 6, and as shown in FIG. 7, a large amount of silver having a very uniform size
  • the nanowires are fabricated. Scanning electron microscopes show that a uniform diameter of silver nanowires is produced, with an average diameter of 40 nm and an average length of 30 ⁇ .
  • Example 9 is a scanning electron microscope for observing the silver nanowires prepared in Example 7.
  • the average diameter is 40 nm
  • the average length is 20 nanowires are produced.
  • Example 10 is a scanning electron micrograph of the silver nanowire manufactured in Example 8, having a short diameter of 70 nm on average, and a uniform size of silver having an average length of
  • Example 11 is a scanning electron micrograph of the silver nanowires prepared in Example 9, having a mean diameter of 90 nm, and a uniform size of silver having an average length of 35 m.
  • Example 12 is a scanning electron micrograph of the silver nanowire manufactured in Example 10, and it was confirmed that a uniform size silver nanowire having an average length of 100 nm and an average length of 50 m was manufactured.
  • 13 and 14 are scanning electron microscopes of silver nanowires prepared in Example 11.
  • the nanowires were manufactured, and among the products recovered by the centrifugation, it was confirmed that the weight percentage occupied by the nanowires was 50 wt% or less.

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Abstract

본 발명의 제조방법은 은염; 수용성 고분자; 계면활성제 또는 표준환원전위가 -0.1 내지 -0.9V인 금속 이온의 할로겐화물인 금속촉매; 및 환원성 용매;를 함유하는 전구체용액을 가열하여 Ag 나노와이어를 제조하는 특징이 있으며, 나노와이어의 합성 시간이 극히 단축되는 효과가 있으며, 미반응되어 버려지는 은전구체의 양을 효과적으로 억제하여 높은 효율로 은 나노와이어가 제조되고, 단순 스케일업에 의해 은 나노와이어를 대량 생산할 수 있다.

Description

명세서
발명의명칭:은나노와이어의제조방법 기술분야
[1] 본발명은은나노와이어의제조방법에관한것으로，상세하게는액상화학법을 이용하여극히단시간내에은나노와이어를대량생산하는방법에관한것이며， 크기가균일하며길이가 lOjtmi이상인고품질의은나노와이어를대량생산하는 방법에관한것이며,투입된대부분의은전구체가은나노와이어로제조되는 매우높은효율을갖는은나노와이어이제조방법에관한것이다.
배경기술
[2] 귀금속단결정나노와이어는그화학적안정성이높고，열전도도및
전기전도도가커전기，자기，광학소자및센서에의활용가치가높다.
[3] 특히은 (Ag)은모든금속중에서가장좋은전기및열전도율을가지고있으며, 가시광영역에서가장높은표면증강라만효율을갖는등광학적특성또한 매우우수하다.
[4] 이러한은 (Ag)을나노와이어형태로제조할경우마이크로전자소자부터
투명전극까지많은웅용에발전을기대할수있으며,광학，화학또는바이오 센서로의활용또한기대되고있다.
[5] 그러나，은나노와이어가다양한분야에활용되기위해서는，균일한굵기，
깨끗한표면,고종횡비및잘정의된크기를가지며크기편차가작은
나노와이어를완화된조건으로대량생산하는기술이가장중요하다.
[6] 상술한바와같이은나노와이어의전기，자기，광학소자，센서로의활용가치가 매우높으나，미국공개특허제 2007-0034052호와같이통상적으로사용되는 액상화학법을이용한은나노와이어합성법은나노와이어의크기및형상 조절이어려우며，제조되는나노와이어의크기편차가매우심하고，반웅시간이 길고대량생산이극히힘든단점이있다.
[7]
발명의상세한설명
기술적과제
[8] 본발명의목적은상압저온의 액상화학법을이용하여,극히단시간내에매우 높은효율로은나노와이어를제조하는방법을제공하는것이며，직경이매우 균일하며,제조되는나노와이어의직경편차가작고， 5 /m이상의길이를가지며， 높은장단축비를갖는은나노와이어를제조하는방법을제공하는것이며,미 반웅되어버려지는은전구체의양을효과적으로억제하여높은효율로은 나노와이어가제조되고，단순스케일업에의해은나노와이어가대량생산되는 은나노와이어의제조방법을제공하는것이며，은나노입자,은나노플레이트및 은나노로드와같이원치않는형상의은생성물이방지되며높은효율로은 나노와이어가제조되고은나노와이어의대량생산가능한은나노와이어의 제조방법을제공하는것이다. 과제해결수단
이하첨부한도면들을참조하여본발명의제조방법을상세히설명한다.
다음에소개되는도면들은당업자에게본발명의사상이충분히전달될수 있도록하기위해예로서제공되는것이다.이때,사용되는기술용어및과학 용어에있어서다른정의가없다면,이발명이속하는기술분야에서통상의 지식을가진자가통상적으로이해하고있는의미를가지며 ,하기의설명및 첨부도면에서본발명의요지를불필요하게흐릴수있는공지기능및구성에 대한설명은생략한다.
본발명에따른은나노와이어의제조방법은은염;수용성고분자；계면활성제 또는표준환원전위가 -0.1내지 -0.9 V인금속이온의할로겐화물인금속촉매;및 환원성용매;를함유하는전구체용액을가열하여은 (Ag)나노와이어를제조하는 특징이있다.
은염，수용성고분자，금속촉매및환원성용매를함유하는전구체용액올 가열하여은 (Ag)나노와이어를제조하는본발명의제조방법에 있어,상기 환원성용매는하나이상의산소원자를포함하는극성용매이다.
상세하게,상기환원성용매는에틸렌글리콜 (Ethylene Glycol),
다이에틸렌글리콜 (Diethylene Glycol), 1,2-프로필렌글리콜 (1,2-propylene glycol), 1,3-프로필렌글리콜 (1,3-propylene gylcol),글리세롤 (glycerol)및
글루코스 (glucose)에서하나이상선택된것이바람직하다.이는환원력제어를 통한나노와이어직경조절，길이조절，반웅속도조절을위함이다.
본발명의제조방법은상기계면활성제를이용하여，스케일업 (scale-up)시에도 극히단시간내에은나노와이어를대량생산할수있으며，투입되는은염의은 90몰%이상이은나노와이어로변환되며,고농도의은전구체용액으로부터 균일한크기를갖는은나노와이어를제조할수있는장점이있다.
본발명의제조방법은상기금속촉매를이용하여，합성되는은생성물의총 증량에서은나노와이어가차지하는증량 %가 95중량 %이상,보다특징적으로 99중량 %이상인특징이있다.
상기계면활성제는음이온성계면활성제,양이온성계면활성제및양쪽성 계면활성제에서하나이상선택된특징이 있다.
보다특징적으로,상기음이온성계면활성제는친수성부분이카르복실산염， 황산염 (sulfate salt),술폰산염 (sulfonate salt),또는이들의혼합물이며，
바람직하게，상기음이온성계면활성제는하기의화학식 1，화학식 2또는 화학식 3으로표시된다.
(화학식 1) [19] Ri-COONa
[20] (화학식 2)
Figure imgf000005_0001
[22] (화학식 3)
[23] R2— S03Na
[24] (상기 R,은 서로 독립적으로，탄소수 10~20의 알킬기 또는 탄소수 10~20의 알케닐기 이며 , 상기 n은 1~5의 정수이며 , 상기 R2는 탄소수 12~20의 알킬기， 탄소수 12-20의 알케닐기 또는 탄소수 12~20의 알킬아릴기 이다.)
[25] 상기 양이온성 계면활성 제는 친수성부분이 1~3급 아민을 함유하는 아민염 , 4급 암모늄염，오늄화합물 또는 이들의 흔합물이며，상기 4급 암모늄염은 함 질소화합물로서 사슬형 알킬과 결합한 것 뿐 만 아니 라 고리형 질소화합물의 함 질소 헤테로 고리화합물을 포함한다. 상기 오늄화합물은 포스포늄，술포늄염 또는 이들의 흔합물을 포함하며 , 상기 함 질소 헤 테로 고리화합물은 피 리듐염 , 퀴놀륨，이미다졸륨 또는 이들의 흔합물을 포함한다.
[26] 바람직 하게，상기 양이온성 계면활성 제는 에스테르를 포함하는 4급
암모늄염 (EQ; ester-containing quaternary ammonium salt)，아미드 및 에스테르를 포함하는 4급 암모늄염 (amide group and ester group in Quaternary Ammonium salts), 피 리 디늄 유도체 (pyridinium derivatives), 베타인 유도체, 이미다졸륨 유도체, 퀴놀리늄 유도체 (quinolinium derivatives), 피 페라지늄
유도체 (piperazinium derivatives) 및 모폴리늄 유도체 (morpholinium
derivatives)에서 하나 이상 선택된 것이다.
[27] 상기 계면활성 제는 상용화된 물질을 사용할 수 있으며，일 예로，
에 이 케 이 켐 텍사의 LDBAC(ASCO®), IMQ(ASCO®), EQ(ASCO®), EAQ(ASCO®), CTAC(ASCO«), 24-3/28(ASCO®), 1416(ASCO®), BT(ASCO®) 또는 ZW(ASCO®)와 같은 시판 계면활성 제를 사용할 수 있다.
[28] 보다 구체적으로，상기 음이온성 계면활성 제는 소디움 라우레스
설페 이트 (Sodium Laureth Sulfate), 소디움 (C14-C16)올레핀 술포네이트 (Sodium (C14-C16) olefin sulfonate) 및 도데실 벤젠 술포네이트 (Sodium dodecyl benzene sulfonate)에서 하나 이상 선택된 것이 다.
[29] 상기 양이온성 계면활성 제는 보다 구체적으로，하기 의 화학식 4, 화학식 5， 화학식 6, 화학식 7，화학식 8, 화학식 9 및 화학식 10에서 하나 이상 선택된 것이 다.
[30] (화학식 4)
Figure imgf000006_0001
[32] (화학식 5)
Figure imgf000006_0002
[36] (화학식 7)
Figure imgf000006_0003
[38] (화학식 8)
[39] Ri i / " Ri
N N
Rio^-- ^ Rio
[40] (화학식 9)
Figure imgf000006_0004
[42] (화학식 10)
Figure imgf000006_0005
[44] (상기 R3, R4, R6 및 R10은 서로 독립적으로 탄소수 1~5의 알킬기 이며 , 상기 R5, R7 , R8, R9 및 R13은 서로 독립 적으로 탄소수 10~20의 알킬기 또는 탄소수 10~20의 알케닐기 이며，상기 Ru은 탄소수 12-20의 알킬기 또는 탄소수 12-20의 알케닐기이며，상기 Rl2는탄소수 1ᅳ3의알킬기이며，상기 p및 q는서로
독립적으로 1~4의정수이며，상기 W,, W2, W3및 W4는서로독립적으로 0， S 또는 NH이며，상기 Χ,-, Χ2-, Χ3% Χ4-, Χ5-및 Χ6ᅳ은서로독립적으로 C1-또는 CH: oso3-이다.)
[45] 상기양쪽성계면활성제는하기의화학식 11및화학식 12에서하나이상
선택된것이다.
[46] (화학식 11)
Figure imgf000007_0001
Y1+
[48] (화학식 12)
Figure imgf000007_0002
[50] (상기 Rl4및 RJ7은서로독립적으로탄소수 12-20의알킬기또는탄소수
12~20의알케닐기이며，상기 R,5는 COO-, P03H-또는 S03-이며，상기 R16은수소 또는탄소수 1~10의알킬기또는탄소수 1~10의알케닐기이며，상기 R18은 OCOO -,OP03H,OS03-또는 S03-이며,상기 r,s및 t는서로독립적으로 1~5의정수이며， 상기 Xf 및 X8-은서로독립적으로 C1-또는 CH3OS03-이며 ,상기 Y,+및 Υ2 +는서로 독립적으로 Na+, K+또는 Li+이다.)
[51] 발명에따른제조방법에서，상기계면활성제는은나노와이어의합성시，가장 크게반웅시간에영향을미치며，나아가，반웅에의해제조되는은생성물의 형상，은나노와이어의크기 (직경,길이)편차,스케일업에의한대량생산 가능성，나노와이어합성시의반웅효율에영향을미친다.
[52] 보다상세하게,본발명에따른계면활성제를채택함으로써，대량생산시에도 극히단시간내 (30분이내)에나노와이어형상의은을제조할수있으며,은 나노와이어합성수율 (yield)을증가시키며，단일한합성에의해동시에제조되는 다수개의은나노와이어들의크기를고르게제어할수있는특징이있다.
[53] 또한，본발명의제조방법에의해은나노와이어의합성시고도의기술적 변경 없는단순스케일업 (scale up)으로，제조되는은나노와이어의생산량을 획기적으로증가시킬수있는특징이 있으며，반웅시투입되는은염의은 나노와이어로의반웅효율또한크게증가되는특징이있다.
[54] 보다상세하게，본발명에따른계면활성제를채택함으로써，상기은염의
형태로투입된은 (Ag)의 90% (몰 %)이상이상기은나노와이어로제조되는매우 높은반응효율 (conversion efficiency)을갖는특징이있으며 ,본발명에따른 계면활성제를채택함으로써은나노와이어제조에필요한합성시간이놀랍도록 단축되는효과가있으며,스케일업에의한대량생산시에도 30분이내의매우 짧은시간내에대량의은나노와이어가제조되는특징이 있다.
[55] 상기은염：계면활성제의중량비는 100： 0.01내지 15인것이바람직하며， 100:
1내지 15인것이보다더바람직하다.은염 100중량을기준으로한
계면활성제의양이 0.001중량부미만인경우，상술한계면활성제의첨가에의한 효과를얻기힘들며，1중량부를초과하는경우은나노와이어가합성되지않을 위험이 있으며,오염등의악영향을미칠수있다.
[56]
[57] 본발명에따른제조방법에 있어,전구체용액이표준환원전위가 -0.1내지 -0.9 V인금속이은의할로겐화물을함유함에따라,나노와이어이외의다른은 생성물의합성을방지할수있을뿐만아니라,장단축비 (aspect ratio)가 100 이상인은나노와이어가제조되는특징이 있다.
[58] 상기금속할로겐화물인금속촉매의상기금속이온의표준환원전위가 -0.1 V를초과하거나， -0.9 V미만인경우은나노와이어로의합성율이크게감소할 위험이 있다.
[59] 상세하게，상기금속이은은 Ni2+(표준환원전위 -0.25 V). Co2+(표준환원전위 -0.29 V), Cr3+(표준환원전위 -0.408 V)및 Zn2+(표준환원전위 -0 63 V)에서하나 이상선택된이온이며，상기금속촉매는 Ni2+. Co2+, Cr3+및 Zn2+에서하나이상 선택된이온의할로겐화물인특징이있으며，상기할로겐화물은염화물， 브롬화물，플투오르화물,요오드화물또는이들의흔합물을포함한다.이때，단 시간내에상기은나노와이어로의합성률을보다증진시키기위해，상기 할로겐화물은염화물인것이바람직하다.
[60J 본발명의제조방법에 있어，상기은염：금속촉매의중량비는 100： 0.01내지 1 이며,바람직하게상기은염；금속촉매의증량비는 100： 0.01내지 0.2이다.
[61] 상기은염：금속촉매의중량비는은나노와이어의합성시반웅의스케일과 무관하게반옹에의해생성되는은생성물에은나노입자，은나노플레이트및 은나노로드의생성을방지하며은나노와이어를선택적으로제조할수있는 비율이다.
[62] 본발명에있어，상술한계면활성제또는금속촉매와함께，상기수용성
고분자의분자량을제어하여은나노와이어의길이를증가시키는특징이있다.
[63] 상세하게,상기수용성고분자는은나노와이어의제조시，측면에붙어
와이어를성장시키는역할을수행하며 ,본발명에따른금속촉매와함께상기 수용성고분자의분자량 (Mw)을증가시켜직경의증가를방지하며보다긴 길이의은나노와이어를제조할수있는특징이있다.보다상세하게，수용성 고분자의분자량 (Mw)을 50,000내지 1,500,000으로제어함으로써，평균길이가 30 ΛΠ내지 70 ; 인은나노와이어를제조할수있는특징이 있다.
[64] 상기수용성고분자는폴리비닐피롤리돈，폴리비닐알콜,폴리아크릴아미드, 폴리아크릴산및이들의공중합체에서하나이상선택된물질인것이 바람직하며，보다바람직하게폴리비닐피롤리돈이다.
[65]
[66] 10 이상의길이를가지며，매우큰장단축비를갖는은나노와이어를
제조하기위해서는반웅초기과도한은핵의핵생성을조절하면서도생성된은 핵이용해된은이온과결합하여빠르게일정방향으로성장하여야한다.
[67] 본발명의제조방법은상술한계면활성제또는금속촉매와함께,상기전구체 용액의가열시교반조건및전구체용액의점도를제어하여,제조되는은 나노와이어의길이및장단축비가제어되는특징이있다.
[68] 보다상세하게,본발명의제조방법은상술한계면활성제또는금속촉매와 함께，전구체용액의가열시교반조건을제어하여，은나노와이어의장축 길이 (이하길이)를증진시키는특징이 있으며,전구체용액의점도를제어하여 은나노와이어의단축길이 (이하직경)를감소시키는특징이있다.
[69] 본발명의제조방법에 있어,상기전구체용액의가열에의한은나노와이어의 제조시，상기전구체용액은무교반상태또는하기의관계식 1을만족하는 특징이있다.
[70] (관계식 1)
[71] 0 < V < 50 cm/sec
[72] (상기 V는전구체용액의평균유속이다.)
[73] 상기무교반상태는인위적인교반이수행되지않음을의미하며，외부장치에 의한유속의변화또는난류의발생이이루어지지않음을의미하나，용액내 자연대류는포함한다.
[74] 본발명에따른제조방법은무교반또는관계식 1을만족하도록상기 전구체 용액의교반상태를제어하여제조되는은나노와이어의장축길이를제어하는 특징이있으며 , 10； ωη이상,보다특징적으로 20 m이상의길이를갖는균일한 크기의은나노와이어를제조하는특징이 있다.
[75] 본발명의제조방법에있어,상기전구체용액은증점제를더함유하는특징이 있으며，상기증점제에의해직경이제어된은나노와이어가제조되는특징이 있다.
[76] 상세하게,상기전구체용액의증점제함량은상기증점제와상기환원성
용매의흔합액이상기환원성용매의점도를기준으로 1.1내지 10배의점도를 갖도록하는양인특징이있으며,상기증점제에매우작은은핵이생성되고 길이방향에수직인측면성장 (lateral growth)이억제되어단축길이가 50nm 이하，실질적으로 20내지 50nm인은나노와이어가제조되는특징이 있다.
[77] 은핵의 핵생성을억제하면서도생성된은핵의측면성장을억제하기위해， 상기증점제는폴리에틸렌글리콜인것이바람직하며，상기폴리에틸렌글리콜은 200내지 20000의분자량을가질수있다.
[78] 상술한바와같이，본발명에따른제조방법에 있어，상기계면활성제에의해 극히단시간내에높은전환효율로고른크기의은나노와이어를제조할수 있으며,상기전구체용액의교반상태에의해은나노와이어의장축길이를 제어할수있으며，상기증점제에의해은나노와이어의직경을제어할수있다.
[79] 상술한바와같이，본발명에따른제조방법에 있어，상기계면활성제에의해 극히단시간내에높은전환효율로고른크기의은나노와이어를제조할수 있으며，상기금속촉매에의해은나노와이어이외의은나노로드，은나노입자 및은나노플레이트와같은원치않는생성물의형성을방지하며종횡비가 100 이상인은나노와이어를제조할수있으며，상기전구체용액의교반상태에 의해은나노와이어의장축길이를제어할수있으며,상기증점제에의해은 나노와이어의직경을제어할수있다.
[80] 일예로，상기계면활성제에의해평균직경이 60내지 90nm,평균길이가 5 내지 9/m의나노와이어를제조할수있으며,상기계면활성제와전구체용액의 교반상태를제어하여，평균직경이 40내지 70 nm,평균길이가 10 β 이상，보다 특징적으로 20내지 100 인은나노와이어를제조할수있으며，상기
계면활성제，전구체용액의교반상태및증점제를이용하여평균직경이 20내지 50 nm,평균길이가 10 i이상，보다특징적 20내지 50 zm인은나노와이어를 제조할수있다.
[81] 일예로,상기금속촉매에의해평균직경이 60내지 80nm이며평균길이가 5/m이상，보다특징적으로 8내지 20ΛΠ인은나노와이어의제조가가능하며， 상기금속촉매와상기전구체용액의교반상태를제어하여평균길이가 20 이상，보다특징적으로 20 내지 50 jtrni이며,평균직경이 70내지 lOOnm인은 나노와이어의제조가가능하며,상기금속촉매,전구체용액의교반상태및 증점제에의해평균직경이 60 nm이하，보다특징적으로, 20내지 50 nm이며 , 평균길이가 20 이상，보다특징적으로 20 /im내지 60 ;zm인은나노와이어의 제조가가능하며，상기금속촉매,전구체용액의교반상태및수용성고분자의 분자량을제어하여평균길이가 30 이상，보다특징적으로， 30 urn내지 70 jMn이며，평균직경이 80내지 llOnm인은나노와이어의제조가가능한특징이 있다.
[82]
[83] 보다상세하게,본발명에따른은나노와이어의제조방법은 a)은염 (Ag salt)및 제 1환원성용매를함유하는제 1용액과계면활성제나금속촉매,수용성고분자, 증점제및제 2환원성용매를함유하는제 2용액을제조하는단계; b)상기 제 2용액을가열하는단계;및 c)상기제 2용액에제 1용액을투입하여은 (Ag) 나노와이어를제조하는단계;를포함하여수행되는특징이있다.이때，상기 c) 단계이후， d)고액분리를이용하여제조된은나노와이어를회수하는단계가더 수행될수있다.
[84] 즉，본발명에따른제조방법은상술한계면활성제또는금속촉매를채택함과 동시에,은나노와이어를제조하기위한은전구체로은염을사용하며，은 전구체와계면활성제또는은전구체와금속촉매를분리하여용액화한후， 계면활성제나금속촉매가용해된용액을선택적으로가열하고，계면활성제나 금속촉매가용해된용액과은전구체용액올흔합반웅시켜은나노와이어를 제조하는특징이 있다.
[85] 보다특징적으로,상기 b)단계에서수행되는제 2용액의가열온도는하기의 관계식 2를만족하는특징이 있다.
[86] (관계식 2)
[87] 0.6Tb <Th< 0.9Tb
[88] (상기 Th는제 2용액의가열온도 (0C)이며,상기 Tb는저가알코올 (제 2용액의 저가알코올)의상압끓는점 (°C)이다)
[89] 상기관계식 2의가열온도는은나노와이어의핵생성및성장구동력을
제어하며,상기관계식 2를만족하도록제 2용액의온도를제어하고본발명에 따른계면활성제를사용함으로써，스케일업에의한대량생산시에도 30분 이내의극히짧은반웅시간 (상기제 1용액과제 2용액의흔합후반웅이완료될 때까지소요되는시간)내에매우균일한크기를갖는은나노와이어를고 효율로대량생산할수있는특징이있다.
[9이 이때，상기증점제는상기제 2용액에함유된것이바람직하며，상기제 2용액에 함유된증점제는상기제 2용액의제 2환원성용매의점도를기준으로 1.1내지 10배의점도를갖도록하는양인것이바람직하다.
[91] 상기제 2용액과제 1용액중계면활성제및증점제를함유하는제 2용액의
선택적가열구성과함께，상기제 2용액과상기제 1용액의흔합시상기 제 2용액의온도변화는제조되는은나노와이어의품질및형상에영향을 미친다.
[92] 본발명의제조방법에있어，상기 c)단계시,상기 b)단계의가열에의한
제 2용액의온도가유지되는특징이있다.즉，상기제 2용액의가열상태를 유지하며상기제 2용액에제 1용액을투입하여은 (Ag)나노와이어를제조하는 것이바람직하다.
[93] 바람직하게，상기 c)단계에서상기제 1용액의투입중상기제 2용액의온도 변화는하기의관계식 3을만족하며，보다바람직하게관계식 3-1을만족한다.
[94] (관계식 3)
[95] 0<ΔΤ2<0.1Τ2
[96] (상기 Τ2는 b)단계의가열에의한제 2용액의온도이며,상기 ΔΤ2는상기
제 1용액이상기제 2용액에투입되는동안상기제 2용액의온도변화이다.)
[97] (관계식 3-1)
[98] 0 <ᅀ Τ2 < 0.05Τ2
[99] (상기 Τ2는 b)단계의가열에의한제 2용액의온도이며，상기 ΔΤ2는상기
제 1용액이상기제 2용액에투입되는동안상기제 2용액의은도변화이다.)
[100] 상세하게，스丁2는상기제 2용액이투입되는동안의특정시간에서의제 2용액의 온도 (Tt)에서상기 b)단계의가열에의한온도 (τ2)를뺀값의절대값을의미한다. [101] 본발명의특징에의해，상기제 1용액의투입이완료된후, 30분이내의반웅이 완료되며，상기제 1용액의투입후에도반웅시간동안상기 b)단계의가열에 의한온도가관계식 2를만족하도록유지됨은물론이다.
[102] 이를위해，가열된제 2용액에은전구체를함유하는제 1용액을첨가하는상기 c)단계에서상기제 1용액은상기제 2용액에불연속적으로투입되는것이 바람직하며，상세하게，상기 c)단계에서상기제 1용액은상기제 1용액의 부피 (VI)를기준으로 0.01내지 5부피 %/sec로상기제 2용액에점적투입되는 것이바람직하다.
[103] 상술한바와같이，본발명의제조방법에있어,상기 c)단계에서의교반상태 또한제조되는나노와이어의형상에영향을미침에따라，상기교반상태와 독립적으로상기관계식 3，보다바람직하게는관계식 3-1이만족되는것이 바람직하다.
[104] 본발명에 있어,상기 c)단계에서상기제 1용액의투입및반웅시간동안상기 제 2용액은무교반상태또는관계식 1-1을만족하는특징이있다.
[105] (관계식 1-1)
[106] 0 < V2 < 50 cm/sec
[107] (상기 V2는제 2용액의평균유속이다.)
[108] 상세하게,본발명에 있어，상기제 1용액의투입증및투입후반웅시간동안 상기제 2용액의교반상태를제어하여제조되는은나노와이어의장축길이를 제어할수있으며,균일한크기를갖는나노와이어를제조하는특징이있다.
[109] 상기 c)단계가제 2용액의무교반상태또는관계식 1-1을만족하는상태로
수행됨으로써 ,상기 c)단계에서평균직경이 40내지 70 nm,평균길이가 10 jtrni 이상，보다특징적으로 20내지 100/II1인은나노와이어를제조할수있
[110] 관계식 1-1에서,상기유속은 c)단계에서의제 2용액인유체의평균유속을
의미하며，상기무교반상태는인위적인교반이수행되지않음을의미하며，외부 장치에의한유속의변화또는난류의발생이이루어지지않음을의미하나，용액 내자연대류는포함한다.
[111] 바람직하게,은염，수용성고분자,계면활성제,증점제및환원성용매를
함유하는전구체용액을가열하여은 (Ag)나노와이어를제조하는본발명의 제조방법에 있어,상기환원성용매는하나이상의산소원자를포함하는극성 용매이다.
[112] 상세하게,상기환원성용매는에틸렌글리콜 (Ethylene Glycol), 1,2-프로필렌 글리콜 (1,2-propylene glycol), 1，3-프로필렌글리콜 (1,3-propylene glycol), 다이에틸렌글리콜 (Diethylene Glycol(DEG)(2-Hydroxyethyl Ether),
글리세롤 (glycerol)및글루코스 (glucose)에서하나이상선택된것이바람직하다. 이는환원력제어를통한나노와이어직경조절,길이조절，반웅속도조절을 위함이다.
[113] 보다상세하게，은염을용해하는제 1환원성용매는에틸렌글리콜 (Ethylene Glycol), 1,2-프로필렌글리콜 (1,2-propylene glycol), 1,3-프로필렌
글리콜 ( 1 ,3-propylene glycol),다이에틸렌글리콜 (Diethylene
Glycol(DEG)(2-Hydroxyethyl Ether),글리세롤 (glycerol)및글루코스 (glucose)에서 하나이상선택된것이며，계면활성제및수용성고분자，바람직하게
계면활성제，수용성고분자및증점제를용해하는제 2환원성용매는상기제 1 환원성용매와독립적으로에틸렌글리콜 (Ethylene Glycol), 1,2-프로필렌 글리콜 (1,2-propylene glycol), 1,3-프로필렌글리콜 (1,3-propylene glycol), 다이에틸렌글리콜 (Diethylene Glycol(DEG)(2-Hydroxyethyl Ether),
글리세를 (glycerol)및글루코스 (glucose)에서하나이상선택된것이다.
[114] 이때，혼화성측면에서,상기제 1환원성용매와제 2환원성용매는동일물질인 것이바람직하며，일예로，상기제！환원성용매및제 2환원성용매는에틸렌 글리콜이다.
[115] 상기은염은환원성용매에용해되는은염이면사용가능하며,일예로，
질산은 (silver nitrate),초산은 (silver acetate),과염소산은 (silver perchlorate)및 염화은 (silver chloride)에서하나이상선택된것이다.
[116] 상기수용성고분자는은나노와이어의제조시，측면에붙어와이어를
성장시키는역할을위해채택된것으로，상술한바와같이，
폴리비닐피를리돈 (Poly vinylpyrrolidone),폴리비닐알콜 (Poly vinylalcohol) 폴리아크릴아미드 (polyarylamide),폴리아크릴산 (polyacrylic acid)및이들의 공중합체에서하나이상선택된물질인것이바람직하며,상기수용성고분자의 분자량 (Mw)은 50,000에서 1,500,000인것이바람직하다.
[117] 본발명에따른제조방법에 있어，계면활성제를함유하는경우，은전구체가 용해된용액인제 1용액은 15내지 40중량 %의은염을함유하는특징이있으며， 본발명에따라，고함량의전구물질 (은전구체)를함유하는제 1용액을이용하여 매우빠른시간에높은효율로은나노와이어를제조할수있게된다.이때,상기 제 2용액은 1내지 15중량 %의수용성고분자를함유하는특징이 있으며， 0.005 내지 1중량 %의계면활성제를함유하는특징이 있다.
[118] 상술한바와같이,상기제 1용액및상기제 2용액은은염 :계면활성제의
증량비가 100 :0.01내지 15가되도록혼합되는것이바람직하며,상기 제 2용액에함유된상기증점제는제 1용액에함유된부피의상기제 1환원성용매 및제 2용액에함유된부피의상기제 2환원성용매가흔합된혼합용매의 점도 (25°C기준)를기준으로，상기혼합용매가 1.1내지 10배의점도 (25°C기준)를 갖도록하는양이다.
[119] 본발명에따른제조방법에 있어，계면활성제를함유하는경우，바람직하게，은 전구체가용해된용액인제 1용액의은염함량은 1내지 12중량 <¾이며，이때, 상기제 2용액의수용성고분자함량은 0.5내지 12중량 금속촉매의함량은 0.0001내지 0.02중량%인특징이 있다.
[120] 상술한바와같이，상기제 1용액및상기제 2용액은은염：금속촉매의 중량비가 100:0.01내지 1되도록혼합되는것이바람직하며，상기제 2용액에 함유된상기증점제는제 1용액에함유된부피의상기제 1환원성용매및 제 2용액에함유된부피의상기제 2환원성용매가혼합된혼합용매의
점도 (250C기준)를기준으로，상기혼합용매가 1.1내지 10배의점도 (25°C기준)를 갖도록하는양이다.
[121] 상술한계면활성제，증점제및교반조건과함께,상기제 1용액의은염함량， 상기제 2용액의수용성고분자의함량，상기계면활성제의함량및금속촉매의 함량은단순스케일업 (scale-up)에의해안정적으로은나노와이어를대량생산 할수있게한다.
[122] 본발명은상술한제조방법으로제조된은나노와이어를함유하는투명전극을 제공한다.상기투명전극은태양전지의전면전극을포함한다.본발명에따라 제조된은나노와이어는종횡비가크고，두께가조절되며,균일한크기를가짐에 따라，본발명의투명전극은은나노와이어들의혼합및도포에의해극히 우수하고균일한전기전도도를가지며，소량의은나노와이어를함유하여도 우수한전기전도도를유지하며,광투과성이우수한투명전극인특징이 있다.
[123]
발명의효과
[124] 본발명에따른제조방법은은나노와이어의합성시고도의기술적변경없이 단순스케일업 (scale-up)에의해제조되는은나노와이어의양을획기적으로 증가시킬수있는특징이있으며，합성시간이놀랍도록단축되어，스케일업에 의한대량생산시에도 30분이내의매우짧은시간내에대량의은나노와이어가 제조되는특징이있으며，평균길이의 30%이내의표준편차를갖는균일한 길이의나노와이어를제조할수있는특징이있으며，은나노와이어의길이및 직경의독립적제어가가능한특징이있으며，반웅시투입되는은염의 90몰% 이상이은나노와이어로제조되는특징이 있으며，나노와이어이외의은 나노로드,은나노입자및은나노플레이트와같은원치않는생성물의형성을 방지할수있으며，균일한크기를가지며평균종횡비가 100이상인은
나노와이어의제조가가능한특징이 있다.
[125]
도면의간단한설명
[126] 도 1은실시예 1에서제조된은나노와이어의주사전자현미경사진이며， [127] 도 2는실시예 2에서제조된은나노와이어의주사전자현미경사진이며, [128] 도 3은실시예 1에서제조된은나노와이어의주사전자현미경사진및 EDS 결과이며，
[129] 도 4는실시예 3에서제조된은나노와이어의주사전자현미경사진이며， [130] 도 5는실시예 4에서제조된은나노와이어의주사전자현미경사진이며， [131] 도 6은실시예 5에서제조된은나노와이어의주사전자현미경사진이며, [132] 도 7은실시예 6에서제조된은나노와이어의주사전자현미경사진이며, [133] 도 8은실시예 6에서제조된은나노와이어의고배율주사전자현미경
사진이며，
[134] 도 9는실시예 7에서제조된은나노와이어의주사전자현미경사진이며， [135] 도 10은실시예 8에서제조된은나노와이어의주사전자현미경사진이며， [136] 도 11은실시예 9에서제조된은나노와이어의주사전자현미경사진이며, [137] 도 12는실시예 10에서제조된은나노와이어의주사전자현미경사진이며， [138] 도 13은실시예 11에서제조된은나노와이어의주사전자현미경사진이며, [139] 도 14는실시예 11에서제조된은나노와이어의고배율주사전자현미경
사진이며,
[140] 도 15는비교예에서제조된은나노와이어의주사전자현미경사진이다.
[141]
발명의실시를위한형태
[142] (실시예 1)
[143] 양이온계면활성제름이용하은나노와이어의합성
[144] AgN03(kojima 99.9%) 0.375 g을상온에서 15분간에틸렌글리콜 (EG, 25°C 점도 =16.1 cp) 1 mL에녹여제 1용액을제조하고，폴리비닐피를리돈 (PVP, Mw
55,000) 0.375 g와베타인 (Cocoamidopropyl Bentaine,에이케이켐텍, CAS registry
No.61789-40-0/83138-08-3) ().023 g을 75°C에서 10분간 4 mL의에틸렌
글리콜 (EG)에녹여제 2용액을제조하였다.
[145] 이후， 50 ml등근바닥플라스크에제 2용액을투입하고，오일배쓰 (oil bath)를 이용하여제 2용액을 160°C로가열하고，제 2용액을 250rpm으로교반하며가열된 제 2용액에마이크로피펫을이용하여 0.02m sec의속도로제 1용액을점적 투입하였다.이때제 1용액의점적시제 2용액의온도변화가 ±3°C이내로 유지됨을확인하였다
[146] 제 1용액의첨가가완료되고 5분후，흔합된용액의색이
밀키화이트 (milky white)로변하는것을확인하고상온으로냉각시켜반웅을 종료하였다.
[147] 이후，반웅이종료된용액에과량 (40mL)의아세톤을첨가하여침전을
형성시킨후원심분리하여은나노와이어를침강시키고나서용매층을버린 다음에다시아세론을넣고은나노와이어를재분산시킨후에원심분리하고 용매를버리는과정을 2회반복수행하여제조된은나노와이어를회수하였다.
[148]
[149] (실시예 2)
[150] ᄋ 이온계며환성제및스케임 에의하대량생산
[151] AgN03(kojima 99.9%) 56.25 g올상온에서 20분간에틸렌글리콜 (EG) 150 mL에 녹여제 1용액을제조하고，폴리비닐피를리돈 (PVP,Mw 55,000) 56.25 g과 베타인 (Cocamidopropyl Bentaine,에이케이켐텍, CAS registry No.
61789-40-0/83138-08-3) 3.45 g을 750C에서 30분간 600 mL의에틸렌
글리콜 (EG)에녹여제 2용액을제조하였다.
[152] 이후，직경 20 cm인 2 L반웅기에제 2용액을투입하고，오일배쓰 (oil bath)를 이용하여제 2용액을 160°C로가열하고,제 2용액을 250rpm으로교반하며가열된 제 2용액에마이크로피펫올이용하여 0.08mL/sec의속도로제 1용액을점적 투입하였다.이때제 1용액의점적시제 2용액의은도변화가 ±50C이내로 유지됨을확인하였다
[153] 제 1용액의첨가가완료되고 10분후，혼합된용액의색이
밀키화이트 (milkywhite)로변하는것을확인하고상온으로냉각시켜반웅을 종료하였다.
[154] 이후，은나노와이어를회수하는과정은실시예 1과동일하게수행하였다.
[155]
[156] (실시예 3)
[157] ^이온계^활성제름이용하은나노와이어의합성
[158] AgN03(kojima 99.9%) 0.375 g을상온에서 15분간에틸렌글리콜 (EG) 1 mL에 녹여제 1용액을제조하고,폴리비닐피를리돈 (PVP,Mw 55,000) 0.375 g와
SLES(Sodium Laureth Sulfate,에이케이켐텍, ASCO® 24-3/28, 68585-34-2) 0.023 g을 75°C에서 10분간 4mL의에틸렌글리콜 (EG)에녹여제 2용액을제조하였다.
[159] 이후, 50 ml의등근바닥플라스크에제 2용액을투입하고,오일배쓰 (oil bath)를 이용하여제 2용액을 160°C로가열하고,제 2용액을 250rpm으로교반하며가열된 저 12용액에마이크로피펫을이용하여 0.02mL/sec의속도로제 1용액을점적 투입하였다.이때제 1용액의점적시제 2용액의온도변화가 ±3°C이내로 유지됨을확인하였다.
[160] 제 1용액의첨가가완료되고 5분후,혼합된용액의색이
밀키화이트 (milkywhite)로변하는것을확인하고상은으로냉각시켜반웅을 종료하였다.
[161] 이후，은나노와이어를회수하는과정은실시예 1과동일하게수행하였다.
[162]
[163] (실시예 4)
[164] 은이온계며환성체 스케임 에의하대량생
[165] AgN03(kojima 99.9%) 56.25 g을상온에서 20분간에틸렌글리콜 (EG) 150 mL에 녹여제 1용액을제조하고,폴리비닐피롤리돈 (PVP, Mw 55,000) 56.25 g와
SLES(Sodium Laureth Sulfate,에이케이캠텍, ASCO® 24-3/28, 68585-34-2) 3.45 g을 75°C에서 30분간 600 mL의에틸렌글리콜 (EG)에녹여제 2용액을제조하였다.
[166] 이후，직경 20 cm인 2 L반웅기에제 2용액을투입하고，오일배쓰 (oil bath)를 이용하여제 2용액올 150°C로가열하고,제 2용액을 250rpm으로교반하며가열된 제 2용액에마이크로피펫올이용하여 a08m!Jsec의속도로제 1용액을점적 투입하였다.이때제 1용액의점적시제 2용액의온도변화가 ±5°C이내로 유지됨을확인하였다ᅳ
[167] 제 1용액의 첨가가완료되고 10분후，혼합된용액의색이
밀키화이트 (milkywhite)로변하는것을확인하고상온으로냉각시켜반웅을 종료하였다.
[168] 이후，은나노와이어를회수하는과정은실시예 1과동일하게수행하였다.
[169]
[170] (실시예 5)
[171] 계며환성제 ¾무교빈ᅳ음이용하온나노와이어의함성
[172] 실시예 1의제 2용액을 160°C로가열하고，제 2용액에교반을수행하지않으며 가열된제 2용액에마이크로피펫을이용하여 0.02mL/sec의속도로제 1용액을 점적투입한것을제외하고,실시예 1과동일하게은나노와이어를제조하였다.
[173]
[174] (실시예 6)
[175] 계며환성제및중점제름이용하온나노와이어의합성
[176] 실시예 1의제 2용액의제조시， 4mL의에틸렌글리콜대신, 3.5 mL의
에틸렌글리콜및 0.5 mL의폴리에틸렌글리콜 (PEG, Mw 55，000)을사용하며， 제조된제 2용액을 160°C로가열하고，제 2용액에교반을수행하지않으며,가열된 제 2용액에마이크로피펫을이용하여 0.02mL/sec의속도로제 1용액을점적 투입한것을제외하고，실시예 1과동일하게은나노와이어를제조하였다.
이때， 4.5 mL의에틸렌글리콜과 0.5 mL의폴리에틸렌글리콜이흔합된용매의 25°C에서의점도는 20 cp이었다.
[177]
[178] (실시예 7)
[179] 계며환성제 ¾저속교바음이용하온나노와이어의합성
[180] 실시예 2의제 2용액의제조시， 600 mL의에틸렌글리콜대신， 525 mL의
에틸렌글리콜및 75 mL의폴리에틸렌글리콜 (PEG, Mw 55,000)을사용하며， 제조된제 2용액을 160°C로가열하고,제 2용액을 30rpm으로교반하며가열된 저 12용액에마이크로피펫을이용하여 0.08mL/sec의속도로제 1용액을점적 투입한것을제외하고，실시예 2와동일하게은나노와이어를제조하였다.이때， 675 mL의에틸렌글리콜과 75 mL의폴리에틸렌글리콜이흔합된용매의
25°C에서의점도는 20 cp이었다.
[181]
[182] (실시예 8)
[183] 금속촉매름이용하온나노와이어의함성
[184] AgN03(kojima99.9 %) 0.17 g을상온에서 15분간에틸렌글리콜 (EG, 25°C
점도 =16.1cp) 10mL에녹여제 1용액올제조하고，상온에서
폴리비닐피를리돈 (PVP, Mw 55,000) 0.17 g와 NiCl2.6H200.2 mg을 10 mL의 에틸렌글리콜 (EG)에녹여제 2용액을제조하였다.
[185] 이후，직경 0.5 cm인 50 ml등근바닥플라스크에제 2용액을투입하고,오일 배쓰 (oil bath)를이용하여제 2용액을 160°C로가열하고，제 2용액을 800 rpm으로 교반,가열된제 2용액에마이크로피펫을이용하여 05mL/sec의속도로 제 1용액을점적투입하였다.이때제 1용액의점적시제 2용액의온도변화가
±3°C이내로유지됨을확인하였다.
[186] 교반상태를유지하며,제 1용액의첨가가완료되고 15분후,흔합된용액의 색이밀키화이트 (milky white)로변하는것을확인하고상온으로냉각시켜 반웅을종료하였다.
[187] 이후,반웅이종료된용액에과량 (40mL)의아세톤을첨가하여침전을
형성시킨후원심분리하여은나노와이어를침강시키고나서용매층을버린 다음에다시아세톤을넣고은나노와이어를재분산시킨후에원심분리하고 용매를버리는과정을 2회반복수행하여제조된은나노와이어를회수하였다.
[188] 이때，원심분리에의해회수된생성물에서 99중량 %이상이은나노와이어
생성물임을확인하였다.
[189]
[190] (실시예 9)
[191] 금속촉매및무교바음이용하온나노와이어의함성
[192] 실시예 8에서제 2용액을교반하지않고제 1용액을첨가하고,무교반상태로 제 1용액의 첨가및반웅을완료한것을제외하고，실시예 8과동일하게은 나노와이어를제조하였다.
[193]
[194] (실시예 10)
[195] 금속촉매.무교바 ¾수용성고분자분자량음이용하온나노와이어의함성
[196] PVP(Mw 55,000)대신 PVP(Mw 1,000,000)을사용한것을제외하고실시예 9와 동일하게은나노와이어를제조하였다.
[197]
[198] (실시예 11)
[199] 금속촉매.저속교바및중점제름이용하은나노와이어의함성
[200] AgN03(kojima 99.9 %) 0.17 g^:상온에서 15분간에틸렌글리콜 (EG) 10 ml에 녹여제 1용액을제조하고，상온에서폴리비닐피롤리돈 (PVP,Mw 360,000) 0J7g ZnCl20.1 mg및폴리에틸렌글리콜 (PEG, Mw 400) 5 ml을 10 ml의에틸렌 글리콜 (EG)에녹여제 2용액을제조하고, 30rpm으로제 2용액을교반하며 제 1용액을첨가하고반응시간동안 30rpm을유지한것을제외하고，실시예 9와 동일하게은나노와이어를제조하였다.
[201] 이때, 10mL의에틸렌글리콜과 5mL의폴리에틸렌글리콜이흔합된용매의
25°C점도는 40cp였으며 ,20 mL의에틸렌글리콜과 5 mL의폴리에틸렌글리콜이 혼합된용매의 25°C점도는 30cp이었다. [202]
[203] (비교예)
[204] 0.769V의표주화워저위름갖는금속촉매름이용하은나노와이어의합성
[205] AgN03(kojima99.9 ) 0.17 g을상온에서 I5분간에틸렌글리콜 (EG) 10 mL에 녹여제 1용액을제조하고，상온에서폴리비닐피를리돈 (PVP,Mw 55,000) 0.17 g와 FeCl30.1 mg을 10mL의에틸렌글리콜 (EG)에녹여제 2용액을제조하였다.
[206] 이후，오일배쓰 (oil bath)를이용하여제 2용액을 160oC로가열하고,제 2용액을
800 rpm으로교반，가열된제 2용액에마이크로피펫을이용하여 0.05 mL/sec의 속도로제 1용액을점적투입하였다.이때제 1용액의 점적시제 2용액의온도 변화가 ±3°C이내로유지됨을확인하였다.
[207] 교반상태를유지하며,제 1용액의첨가가완료되고 15분후,혼합된용액의 색이밀키화이트 (milkywhite)로변하는것을확인하고상온으로냉각시켜 반웅을종료하였다.
[208] 이후，반웅이종료된용액에과량 (40mL)의아세톤을첨가하여침전을
형성시킨후원심분리하였으며,이를 2회반복수행하여제조된은
나노와이어를회수하였다.
[209]
[210] 도 1은실시예 1에서제조된은나노와이어를관찰한주사전자현미경
사진으로,도 1에서알수있듯이매우균일한크기를갖는대량의은
나노와이어가제조됨을알수있다.주사전자현미경을통해관찰한결과， 70 nm의평균직경및 7 mi의평균길이를가지며，은나노와이어의길이편차가 8.77로，평균길이의 70.76%이내의편차를갖는균일한크기의은나노와이어가 제조됨을확인하였다.또한，반웅시투입되는은염의 94%가은나노와이어로 전환됨올확인하였다.
[211] 도 2는실시예 2에서제조된은나노와이어의주사전자현미경사진으로, 스케일업에의해서도실시예 1과유사하게균일한크기를갖는은
나노와이어가제조됨을알수있으며 , 30분이내의짧은시간，실시예를 기반하면 10분이내의매우짧은시간내에수; ΜΠ의길이를갖는은
나노와이어가대량생산됨을알수있다.
[212] 도 3(a)는실시예 1에서제조된은나노와이어의주사전자현미경사진이며，도 3(b)는상기도 3(a)의 1내지 4영역에서측정된 EDS(energy dispersive spectroscopy)결과이다.제조된모든나노와이어의모든영역에서유사한 EDS 결과를얻었으며,코팅물질과같이분석을위해부차적으로첨가된물질 (Cu)을 제외하고은 (Ag)만이검출되었다.
[213] 도 4는실시예 3에서제조된은나노와이어를관찰한주사전자현미경
사진이며，도 5는실시예 4에서제조된은나노와이어를관찰한주사전자현미경 사진이다.음이온계면활성제를사용한경우에도양이온계면활성제와유사한 결과를얻을수있었으며,단순스케일업에의해서단시간내에고효율로은 나노와이어가대량생산됨을알수있다.
[214] 도 6은실시예 5에서제조된은나노와이어를관찰한주사전자현미경
사진으로,무교반상태에서나노와이어를제조함으로써，평균직경이 50 nm이며，평균길이가 80卿인은나노와이어가제조됨을확인하였다.
[215] 도 7및도 8은실시예 6에서제조된은나노와이어를관찰한주사전자현미경 사진으로,도 7에서알수있듯이매우균일한크기를갖는대량의은
나노와이어가제조됨을알수있다.주사전자현미경을통해관찰한결과， 40 nm의평균직경및 30 ΛΠ의평균길이를가지며,균일한크기의은나노와이어가 제조됨을알수있다.
[216] 도 9는실시예 7에서제조된은나노와이어를관찰한주사전자현미경
사진으로,도 9에서알수있듯이，저속교반상태에서나노와이어를
제조함으로써，평균직경이 40 nm이며 ,평균길이가 20 인은나노와이어가 제조됨을확인하였다.
[217] 도 10은실시예 8에서제조된은나노와이어의주사전자현미경사진으로，평균 70nm단축직경을가지며 ,평균길이 10 를갖는균일한크기의은
나노와이어가제조됨을확인하였다.
[218] 도 11은실시예 9에서제조된은나노와이어의주사전자현미경사진으로，평균 90 nm단축직경을가지며，평균길이 35 m를갖는균일한크기의은
나노와이어가제조됨을확인하였다.
[219] 도 12는실시예 10에서제조된은나노와이어의주사전자현미경사진으로， 평균 100 nm단축직경을가지며，평균길이 50 m를갖는균일한크기의은 나노와이어가제조됨을확인하였다.
[220] 도 13및도 14는실시예 11에서제조된은나노와이어의주사전자현미경
사진으로，평균 50nm단축직경을가지며,평균 30； «m의길이를갖는균일한 크기의은나노와이어가제조됨을확인하였다.
[221] 도 15는비교예에서제조된은나노와이어의주사전자현미경사진으로,평균
150 nm직경을가지며 ,평균 8 의길이를갖는장단축비가 53인은
나노와이어가제조됨을알수있으며，원심분리에의해회수된생성물중，은 나노와이어가차지하는중량%가 50중량 %이하임을확인하였다.
[222] 이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는본발명의보다전반적인이해를돕기위해서제공된것일 뿐,본발명은상기의실시예에한정되는것은아니며,본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
[223] 따라서 ,본발명의사상은설명된실시예에국한되어정해져서는아니되며， 후술하는특허청구범위뿐아니라이특허청구범위와균등하거나등가적변형이 있는모든것들은본발명사상의범주에속한다고할것이다.

Claims

청구범위
은염 (Ag salt); 수용성 고분자；계면활성제 또는 표준환원전위가 -0.1 내지 -0.9 V인 금속 이온의 할로겐화물인 금속촉매 ; 및 환원성 용매 ;를 함유하는 전구체용액을 가열하여 은 (Ag) 나노와이 어를 제조하는 것올 특징으로 하는 은 나노와이어 의 제조방법 .
제 1항에 있어서，
상기 전구체 용액의 가열에 의 한 은 나노와이어 의 제조는 무교반 상태로 수행되 거나, 하기의 관계식 1을 만족하는 것을 특징으로 하는 은 나노와이어 의 제조방법 .
(관계식 1)
0 cm/sec < V < 50 cm/sec
(상기 V는 전구체 용액의 평균 유속이 다.)
제 1항에 있어서，
상기 전구체용액은 증점 제를 더 함유하는 것을 특징으로 하는 은 나노와이 어의 제조방법 .
제 3항에 있어서，
상기 전구체용액의 증점제 함량은 상기 증점제와 상기 환원성 용매의 흔합액이 상기 환원성 용매의 점도를 기준으로 1.1 내지 10배의 점도를 갖도록 하는 양인 것을 특징으로 하는 은
나노와이 어 의 제조방법 .
제 1항에 있어서 ,
상기 계면활성제는 음이온성 계면활성제, 양이온성 계면활성제 및 양쪽성 계면활성 제에서 하나 이상 선택된 것을 특징으로 하는 은 나노와이어 의 제조방법 .
제 5항에 있어서，
상기 음이온성 계면활성 제는 소디움 라우레스 설페이트 (Sodium Laureth Sulfate), 소디움 (C14-C16)올레핀 술포네 이트 (sodium (C14-C16)olefin sulfonate) 및 소디움 도데실 벤젠
술포네 이트 (Sodium dodecyl benzene sulfonate)에서 하나 이상 선택된을 특징으로 하는 은 나노와이어 의 제조방법 .
제 5항에 있어서，
상기 양이온성 계면활성 제는 에스테르를 포함하는 4급
암모늄염 (EQ; ester-containing quaternary ammonium salt),아口 1드 및 에스테르를 포함하는 4급 암모늄염 (amide group and ester group in Quaternary Ammonium salts), 피 리 디늄 유도체 (pyridinium derivatives), 베타인 유도체, 이 미 다졸륨 유도체, 퀴 놀리늄 유도체 (quinolinium derivatives), 피 페라지늄 유도체 (piperazinium derivatives)및모폴리늄유도체 (morpholinium derivatives)에서하나 이상선택된것을특징으로하는은나노와이어의제조방법.
[청구항 8] 제 1항에있어서，
상기은염：계면활성제의중량비는 100： 0.01내지 15인것을 특징으로하는은나노와이어의제조방법 .
[청구항 9] 제 1항에있어서，
상기금속촉매의금속이은은 NP+. Co2+, Cr3+및 Zn2+에서하나이상 선택된이온인것을특징으로하는은나노와이어의제조방법. [청구항 10] 제 9항에있어서，
상기금속촉매는염화물인것을특징으로하는은나노와이어의 제조방법.
[청구항 11] 제 1항에있어서，
상기은염：금속촉매의중량비는 100： 0.01내지 1인것을 특징으로하는은나노와이어의제조방법.
[청구항 I2] 제 1항에 있어서,
상기수용성고분자는폴리비닐피를리돈，폴리비닐알콜, 폴리아크릴아미드，폴리아크릴산및이들의공증합체에서하나 이상선택된물질에서하나이상선택된것을특징으로하는은 나노와이어의제조방법.
[청구항 B] 제 12항에 있어서，
상기수용성고분자의분자량 (Mw)은 50,000에서 1,500,000인것을 특징으로하는은나노와이어의제조방법 .
[청구항 I4] 제 1항내지제 13항에서선택된어느한항에있어서,
a)은염 (Ag salt)및제 1환원성용매를함유하는제 1용액과수용성 고분자,계면활성제나금속촉매,증점제및게 2환원성용매를 함유하는제 2용액을제조하는단계;
b)상기제 2용액올가열하는단계;및
c)상기제 2용액에제 1용액을투입하여은 (Ag)나노와이어를 제조하는단계;
를포함하는것을특징으로하는은나노와이어의제조방법 .
[청구항 I5] 제 14항에있어서，
상기 b)및 c)단계에서의제 2용액의온도는하기의관계식 2를 만족하는것을특징으로하는은나노와이어의제조방법.
(관계식 2)
0.6Tb <Th< 0.9Tb
(상기 Th는제 2용액의가열온도 (0C)이며,상기 Tb는상기 제 2환원성용매의상압끓는점 (°C)이다)
[청구항 16] 제 15항에있어서， 상기 c)단계에서상기제 1용액의투입중상기제 2용액의온도
변화는하기의관계식 3을만족하는것을특징으로하는은 나노와이어의제조방법.
(관계식 3)
0<ΔΤ2<0.1χΤ2
(상기 Τ2는 b)단계의가열에의한제 2용액의온도 (°C)이며，상기 ΔΤ2는상기제 1용액이상기제 2용액에투입되는동안상기 제 2용액의온도변화이다.)
[청구항 π] 제 14항에 있어서,
상기제 2용액은계면활성제를함유하며,상기 a)단계에서
제 1용액의은염은 15내지 40중량%인것을특징으로하는은 나노와이어의제조방법.
[청구항 18] 제 17항에있어서,
상기 a)단계에서상기제 2용액의수용성고분자는 1내지 15 중량%이며,계면활성제는 0.005내지 1중량%인것을특징으로 하는은나노와이어의제조방법 .
[청구항 I9] 제 14항에 있어서,
상기제 2용액은금속촉매를함유하며，상기 a)단계에서제 1용액의 은염은 1내지 12중량 %인것올특징으로하는은나노와이어의 제조방법.
[청구항 20] 제 19항에있어서，
상기 a)단계에서상기제 2용액의수용성고분자는 0.5내지 12 중량 "¾이며,금속촉매는 0.0001내지 0.02증량 %인것을특징으로 하는은나노와이어의제조방법.
[청구항 21] 제 1항에 있어서,
상기은염은질산은 (silver nitrate),초산은 (silver acetate),
과염소산은 (silverperchlorate)및염화은 (silver chloride)에서하나 이상선택된것을특징으로하는은나노와이어의제조방법.
[청구항 22] 제 1항에 있어서,
상기환원성용매는하나이상의산소원자를포함하는극성 용매인것을특징으로하는은나노와이어의제조방법.
[청구항 23] 제 14항에 있어서,
상기제 1환원성용매및제 2환원성용매는서로독립적으로 에틸렌글리콜 (Ethylene Glycol), 1,2-프로필렌글리콜 (1,2-propylene glycol), 1,3-프로필렌글리콜 (1,3-propylene glycol),
다이에틸렌글리콜 (Diethylene Glycol(DEG)(2-Hydroxyethyl Ether), 글리세롤 (glycerol)및글루코스 (glucose)에서하나이상선택된 것을특징으로하는은나노와이어의제조방법. [청구항 24] 제 3항에있어서，
상기증점제는폴리에틸렌글리콜인것을특징으로하는은 나노와이어의제조방법.
[청구항 25] 제 1항내지제 13항에서선택된어느한항의제조방법으로 제조된은나노와이어를함유하는투명전극.
PCT/KR2011/005426 2010-07-22 2011-07-22 은 나노와이어의 제조방법 WO2012011774A2 (ko)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN103978202A (zh) * 2013-02-08 2014-08-13 智超虹研发有限公司 用于生物检测片的纳米银线组合物、生物检测片及其制作方法
CN104854020A (zh) * 2012-12-14 2015-08-19 茵斯康科技株式会社 使用共聚物封端剂制备银纳米线的方法
US20180287608A1 (en) * 2013-02-26 2018-10-04 C3Nano Inc. Fused metal nanostructured networks, fusing solutions with reducing agents and methods for forming metal networks
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* Cited by examiner, † Cited by third party
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KR101554927B1 (ko) 2014-07-21 2015-09-22 주식회사 에이든 은 나노와이어 제조방법 및 이를 이용한 투명전극
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DE102015013239A1 (de) * 2014-10-28 2016-04-28 Dow Global Technologies Llc Hydrothermalverfahren zur Herstellung von Silber-Nanodrähten
CN106345997A (zh) * 2016-09-30 2017-01-25 天津宝兴威科技有限公司 一种形貌均一的超细银纳米线及其制备方法
CN106493383A (zh) * 2016-09-30 2017-03-15 天津宝兴威科技有限公司 一种长度为30μm纳米银线的合成方法
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JP2018071000A (ja) * 2016-10-25 2018-05-10 Ｄｏｗａエレクトロニクス株式会社 銀ナノワイヤの製造方法
CN107199114B (zh) * 2017-05-22 2019-04-19 哈尔滨工业大学 制备银纳米线透明电极的选择性去除不均匀短线的方法
US20200390908A1 (en) * 2017-11-04 2020-12-17 Sona Nanotec Metal Nanoparticles and Methods of Making Same
US10714230B2 (en) * 2017-12-06 2020-07-14 C3Nano Inc. Thin and uniform silver nanowires, method of synthesis and transparent conductive films formed from the nanowires
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CN110756822B (zh) * 2019-10-16 2022-05-20 西安工业大学 一种针形银纳米线及其制备方法
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CN114226748B (zh) * 2021-12-21 2023-10-24 深圳市华科创智技术有限公司 一种银纳米线的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155674A (ja) * 2007-12-25 2009-07-16 Osaka Univ 金属のナノ粒子を製造する方法
JP2009203484A (ja) * 2008-02-26 2009-09-10 Achilles Corp ワイヤー状の金属粒子の合成方法
KR20100055983A (ko) * 2008-11-18 2010-05-27 광 석 서 이온성 액체를 이용한 금속 나노와이어의 제조방법

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7575621B2 (en) 2005-01-14 2009-08-18 Cabot Corporation Separation of metal nanoparticles
CN1709791A (zh) 2005-07-05 2005-12-21 华东理工大学 一种制备银纳米线的方法
CN101971354B (zh) * 2007-04-20 2012-12-26 凯博瑞奥斯技术公司 高对比度的透明导体及其形成方法
US7922787B2 (en) * 2008-02-02 2011-04-12 Seashell Technology, Llc Methods for the production of silver nanowires
US9574272B2 (en) * 2008-09-02 2017-02-21 Ramot At Tel-Aviv University Ltd Metal nanowire thin-films
CN101451270B (zh) * 2008-12-11 2011-04-13 常振宇 一种大批量制备贵金属纳米线的方法
US20100242679A1 (en) * 2009-03-29 2010-09-30 Yi-Hsiuan Yu Method for continuously fabricating silver nanowire

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155674A (ja) * 2007-12-25 2009-07-16 Osaka Univ 金属のナノ粒子を製造する方法
JP2009203484A (ja) * 2008-02-26 2009-09-10 Achilles Corp ワイヤー状の金属粒子の合成方法
KR20100055983A (ko) * 2008-11-18 2010-05-27 광 석 서 이온성 액체를 이용한 금속 나노와이어의 제조방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GOU, LINFENG ET AL.: 'Convenient, rapid synthesis of Ag nanowires.' CHEM. MATER. vol. 19, 2007, pages 1755 - 1760 *
SUN, YUGANG ET AL.: 'Large-scale synthesis of uniform silver nanowires through a soft, self-seeding, polyol process.' ADVANCED MATERIALS. vol. 14, no. 11, 2002, pages 833 - 837 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102692405A (zh) * 2012-06-07 2012-09-26 中国科学院合肥物质科学研究院 米粒状氟化物/银复合纳米材料、制备方法及应用
CN104854020A (zh) * 2012-12-14 2015-08-19 茵斯康科技株式会社 使用共聚物封端剂制备银纳米线的方法
CN103978202A (zh) * 2013-02-08 2014-08-13 智超虹研发有限公司 用于生物检测片的纳米银线组合物、生物检测片及其制作方法
EP2765201A1 (en) * 2013-02-08 2014-08-13 K Cubic Research Co., Ltd Silver nanowire-containing composition, biosensor strip comprising the same and its preparation method
US20180287608A1 (en) * 2013-02-26 2018-10-04 C3Nano Inc. Fused metal nanostructured networks, fusing solutions with reducing agents and methods for forming metal networks
CN110983444A (zh) * 2019-11-05 2020-04-10 复旦大学 一种制备Ag-BHT单晶纳米线的方法

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