US20130160608A1 - Process For Producing Silver Nanowires - Google Patents

Process For Producing Silver Nanowires Download PDF

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US20130160608A1
US20130160608A1 US13/807,337 US201113807337A US2013160608A1 US 20130160608 A1 US20130160608 A1 US 20130160608A1 US 201113807337 A US201113807337 A US 201113807337A US 2013160608 A1 US2013160608 A1 US 2013160608A1
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reaction mixture
silver
chemical
forms
salt
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Robert Nusko
Georg Maier
Theo Kaiser
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RENT A SCIENTIST GmbH
Heraeus Deutschland GmbH and Co KG
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Heraeus Precious Metals GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a process for the production of silver nanowires.
  • silver nanowire is a collective term for all materials which
  • a synthesis route for the production of silver nanowires by the polyol process in which an organic chemical which is adsorbed on to the silver surface (preferably polyvinylpyrrolidone—PVP), small amounts of a halide (preferably chloride in the form of NaCl), small amounts of an Fe(II) or Fe(III) salt (preferably Fe(III) acetylacetonate) and a silver salt (preferably AgNO 3 ) are employed in addition to a hot polyol (preferably ethylene glycol), is to be found in the abovementioned prior art.
  • a hot polyol preferably ethylene glycol
  • the addition of an acid preferably HCl or HNO 3
  • the sequence of addition of the various chemicals, reaction temperatures, concentrations and concentration ratios stated are sometimes different or contradictory.
  • K. E. Korte et al. discloses the production of silver nanowires by a polyol process. Copper in the form of CuCl or CuCl 2 is employed as the chemical which forms a redox pair.
  • the essential finding from (1) is that the Cu removes the O from the 111 sites of the Ag surface and in this way renders possible the 1D growth.
  • a reaction mixture comprises a polyol, an organic chemical adsorbed on to a silver surface, a chemical which forms one or more of a halide and a pseudohalide, wherein the chemical which forms a halide is a salt of one or more of the halides Cl ⁇ , Br ⁇ and I ⁇ and wherein the chemical which forms a pseudohalide is a salt of one or more of the pseudohalides SCN ⁇ , CN ⁇ , OCN ⁇ and CNO ⁇ and a chemical which forms a redox pair, the chemical selected from the group consisting of bromine, iodine, vanadium and mixtures thereof.
  • a silver salt is added to the reaction mixture in an amount such that the concentration of silver in the reaction mixture is at least 0.5 wt. %, based on the total weight of the reaction mixture.
  • the silver salt is added at a temperature of the reaction mixture of at least 100° C.
  • the temperature of the reaction mixture is maintained at least 100° C. for the duration of the reaction.
  • the silver salt is added in an amount such that the concentration of silver in the reaction mixture is at least 1.0 wt. %, preferably at least 2.5 wt. %, particularly preferably at least 5.0 wt. %, based on the total weight of the reaction mixture.
  • the reaction mixture comprises one or more of the chemical which forms the halide and the chemical which forms the pseudohalide in an amount such that the concentration of the halide and/or the pseudohalide in the reaction mixture is in a range of from 5 ppm to 2,000 ppm, preferably in a range of from 20 ppm to 1,000 ppm, particularly preferably in a range of from 50 ppm to 500 ppm.
  • the chemical which forms the halide comprises one or more of NaCl, NaBr, NaI, KCl, KBr and KI. In one or more embodiments, the chemical which forms the pseudohalide comprises one or more of NaSCN and KSCN.
  • the reaction mixture provided in step a) additionally comprises an iron salt, the iron salt forming an Fe(II)/Fe(III) redox pair.
  • the reaction mixture provided in step a) additionally comprises a copper salt, the copper salt forming a redox pair.
  • the reaction mixture provided in step a) additionally comprises at least one inorganic or organic acid.
  • the acid comprises one or more of HCl, HBr, HI and HNO 3 .
  • the addition of the acid takes place in an amount such that the concentration of acid in the reaction mixture is in a range of from 0.01 wt. % to 2.0 wt. %, based on the total weight of the reaction mixture.
  • the chemical which forms a redox pair comprises one or more of elemental vanadium, a vanadium oxide, a vanadium hydroxide, a vanadium sulphate, a vanadium nitrate, a vanadium chloride and mixtures of these compounds.
  • the redox pair comprises one or more of Br ⁇ /Br 2 /BrO 3 ⁇ , I ⁇ /I 2 /IO 3 ⁇ and/or V(0)/V(II)/V(III)/V(IV)/V(V).
  • the concentration in the reaction mixture of the chemical which forms a redox pair is in a range of from 5 ppm to 2,000 ppm, preferably in a range of from 20 ppm to 1,000 ppm, particularly preferably in a range of from 50 ppm to 500 ppm.
  • the silver salt is added at a temperature of the reaction mixture of at least 145° C., preferably at a temperature of the reaction mixture of between 145° C. and 200° C., particularly preferably at a temperature of the reaction mixture of between 150° C. and 180° C., especially preferably at a temperature of the reaction mixture of between 155° C. and 170° C.
  • step c) the temperature of the reaction mixture of at least 145° C., preferably a temperature of the reaction mixture of between 145° C. and 200° C., particularly preferably a temperature of the reaction mixture of between 150° C. and 180° C., especially preferably a temperature of the reaction mixture of between 155° C. and 170° C. is maintained for the duration of the reaction.
  • step c) step d) isolating silver nanowires from the reaction mixture, wherein a suitable solvent is added for isolation of the silver nanowires from the reaction mixture and the supernatant is then decanted off.
  • step c) and before step d) step c 1 ) cooling the reaction mixture to room temperature.
  • a reaction mixture is prepared comprising a polyol, an organic chemical adsorbed onto a silver surface, a chemical which forms one or more of a halide and a pseudohalide, a chemical which forms a redox pair and at least one of an inorganic acid and an organic acid.
  • the chemical which forms a halide is a salt of one or more of the halides Cl ⁇ , Br ⁇ and I ⁇ and the chemical which forms a pseudohalide is a salt of one or more of the pseudohalides SCN ⁇ , CN ⁇ , OCN ⁇ and CNO ⁇ and is present in the range of about 5 ppm to about 2000 ppm.
  • the chemical which forms a redox pair is selected from the group consisting of bromine, iodine, vanadium and mixtures thereof.
  • a silver salt is added to the reaction mixture at a temperature of at least 100° C.
  • the silver salt is present in a concentration of at least 0.5 wt. % based on the total weight of the reaction mixture.
  • the reaction mixture is maintained at a temperature of at least 100° C. for the duration of the reaction to form silver nanowires.
  • the reaction mixture is cooled to about room temperature.
  • the silver nanowires are isolated from the reaction mixture comprises adding a suitable solvent to the cool reaction mixture and decanting off a supernatant.
  • FIG. 1 shows a scanning electron micrograph of silver nanowires prepared in accordance with one or more embodiments of the invention.
  • Embodiments of the invention provide processes for the production of silver nanowires which are carried out at a high reaction concentration of silver and which deliver a high yield of silver nanowires.
  • Embodiments of the invention provide processes for the production of silver nanowires.
  • the process comprises the steps:
  • the processes according to one or more embodiments the invention for the production of silver nanowires are a polyol synthesis, in which a silver salt is reduced in the hot polyol in the presence of an organic chemical which is adsorbed on to the silver surface, a chemical which forms a halide and/or one which forms a pseudohalide, and a chemical which forms a redox pair, chosen from the group of bromine, iodine, vanadium and mixtures thereof, to give metallic silver in the form of nanowires.
  • the process according to one or more embodiments of the invention renders possible the production of silver nanowires in a high yield of 80% and more with a simultaneously high reaction concentration of silver of at least 0.5 wt. %, based on the total weight of the reaction mixture.
  • the end of the reaction can be determined by the person skilled in the art without problems, since on the one hand the formation of the silver nanowires can be easily monitored visually, and on the other hand the evolution of gas occurring during the reaction ceases. At the end of the reaction, a nacreous, iridescent dispersion is present.
  • reaction mixture constituents a chemical which forms a halide and/or one which forms a pseudohalide” and “chemical which forms a redox pair, chosen from the group consisting of bromine, iodine, vanadium and mixtures thereof” overlap.
  • the redox pair forming chemicals bromine and iodine are halogens which, in the form of one of their salts, are both a “salt of a halide” and a “chemical which forms a redox pair, chosen from the group consisting of bromine and iodine”.
  • compounds such as, for example, NaBr or VCl 3 , are in fact capable of fulfilling the tasks of the two constituents of the reaction mixture.
  • the silver salt is added in an amount such that the concentration of silver in the reaction mixture is at least 1.0 wt. %, preferably at least 2.5 wt. %, particularly preferably at least 5.0 wt. %, based on the total weight of the reaction mixture. As the concentration of silver in the reaction mixture increases, the amount of silver nanowires which are produced in one working operation increases, with a constant yield.
  • the reaction mixture comprises the chemical which forms the halide and/or the chemical which forms the pseudohalide in an amount such that the concentration of the halide and/or of the pseudohalide in the reaction mixture is in a range of from 5 ppm to 2,000 ppm, preferably in a range of from 20 ppm to 1,000 ppm, particularly preferably in a range of from 50 ppm to 500 ppm.
  • the chemical which forms the halide is NaCl, NaBr, NaI, KCl, KBr and/or KI.
  • the chemical which forms the halide is elemental bromine and/or elemental iodine.
  • the chemical which forms the pseudohalide is NaSCN and/or KSCN.
  • the reaction mixture provided in step a) additionally comprises an iron salt, the iron salt forming an Fe(II)/Fe(III) redox pair in the reaction mixture.
  • the iron salt added is thus capable of forming an Fe(II)/Fe(III) redox pair under the reaction conditions of the process according to the invention.
  • the reaction mixture provided in step a) additionally comprises a copper salt, the copper salt forming a redox pair in the reaction mixture.
  • the copper salt added is thus capable of forming a redox pair under the reaction conditions of the process according to the invention.
  • the chemical which forms a redox pair is elemental vanadium, a vanadium oxide, a vanadium hydroxide, a vanadium sulphate, a vanadium nitrate, a vanadium chloride or a mixture of these compounds.
  • the redox pair is Br ⁇ /Br 2 /BrO 3 ⁇ , I ⁇ /I 2 /IO 3 ⁇ and/or V(0)/V(II)/V(III)/V(IV)/V(V).
  • the concentration in the reaction mixture of the chemical which forms a redox pair is in a range of from 5 ppm to 2,000 ppm, preferably in a range of from 20 ppm to 1,000 ppm, particularly preferably in a range of from 50 ppm to 500 ppm.
  • the reaction mixture provided in step a) additionally comprises at least one inorganic or organic acid.
  • the acid is HCl, HBr, HI and/or HNO 3 .
  • the acid is added in an amount such that the concentration of acid in the reaction mixture is in a range of from 0.01 wt. % to 2.0 wt. %, preferably in a range of from 0.02 wt. % to 1.0 wt. %, particularly preferably in a range of from 0.05 wt. % to 0.5 wt. %, based on the total weight of the reaction mixture.
  • the silver salt is added at a temperature of the reaction mixture of at least 145° C., preferably at a temperature of the reaction mixture of between 145° C. and 200° C., particularly preferably at a temperature of the reaction mixture of between 150° C. and 180° C., especially preferably at a temperature of the reaction mixture of between 155° C. and 170° C.
  • a temperature of the reaction mixture of at least 145° C. preferably a temperature of the reaction mixture of between 145° C. and 200° C., particularly preferably a temperature of the reaction mixture of between 150° C. and 180° C., especially preferably a temperature of the reaction mixture of between 155° C. and 170° C. is maintained for the duration of the reaction.
  • step d) isolation of the silver nanowires from the reaction mixture is carried out, wherein a suitable solvent is preferably added for isolation of the silver nanowires from the reaction mixture and the supernatant is then decanted off.
  • a suitable solvent is preferably added for isolation of the silver nanowires from the reaction mixture and the supernatant is then decanted off.
  • the solvents deionized water, ethanol or isopropanol are added.
  • step c 1 cooling of the reaction is mixture is carried out, wherein cooling of the reaction mixture to room temperature preferably takes place.
  • the processes disclosed are based on the polyol process. This means that compounds having several hydroxyl groups are employed as the solvent and reducing agent.
  • all polyols which are capable of reducing the silver compound employed to elemental silver can be employed. It is possible to use a single polyol in the reaction mixture, or a mixture of two, three, four, five or more polyols.
  • the polyols can have two, three, four, five or more hydroxyl groups, and in addition hetero atoms, such as, for example, oxygen or nitrogen. These hetero atoms can be present in the form of an ether, ester, amine and/or amide function.
  • the polyol can thus be a polyester polyol, a polyether polyol or a similar compound.
  • the polyol can be either an aliphatic glycol or a corresponding glycol polyester.
  • Possible aliphatic glycols are, in particular, alkylene glycols having up to 6 carbon atoms in the main chain. Examples of such compounds are ethanediol, a propanediol, a butanediol, a pentanediol or a hexanediol, and also polyalkylene glycol derivatives of these alkylene glycols.
  • the polyol can comprise, for example, two, three, four, five or six hydroxyl groups and two, three, four, five, six, seven, eight, nine, ten, eleven or twelve carbon atoms.
  • the (alkylene) polyol can be a glycol, that is to say a compound having hydroxyl groups on adjacent (aliphatic or cycloaliphatic) carbon atoms.
  • the glycols can contain, for example, two, three, four, five or six carbon atoms.
  • Preferred polyols are glycerol, trimethylolpropane, pentaerythritol, triethanolamine and trihydroxymethylaminomethane.
  • polyols ethylene glycol, diethylene glycol, triethylene glycol, propylene glycols, butanediols, dipropylene glycols and a polyethylene glycol which is liquid at the reaction temperature, such as, for example, polyethylene glycol 300 , are likewise preferred.
  • Particularly preferred polyols are tetraethylene glycol, 1,2-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 2,3-butanediol.
  • the glycols mentioned have a high reducing power, a boiling point of between 185° C. and 328° C., a good heat stability and low acquisition costs.
  • a further group of polyols which is suitable for use in processes according to the present invention comprises: ethylene glycol, glycerol, glucose, diethylene glycol, triethylene glycol, propylene glycols, butanediol, dipropylene glycol and polyethylene glycols.
  • polyols such as, for example, sugars and alcohols, by themselves or in the form of mixtures, can also form at least a part of the polyol reactants.
  • polyols which are liquid at room temperature and at the corresponding reaction temperature are used, but this is not absolutely necessary.
  • polyols which are solid or semi-solid at room temperature can be employed.
  • solvents from the group of polar protic solvents such as e.g. water, alcohols and aldehydes and mixtures thereof, are additionally employed.
  • reducing agents in addition to the polyol from the group of alcohols, aldehydes, ketones, amines and tartrates, citrates, hydrides, hydrazine and its compounds, are suitable in particular for the production of the nanowires according to the invention.
  • ethylene glycol ethane-1,2-diol
  • glycerol propane-1,2,3-triol
  • the silver salt provides the silver ions for the reduction. Suitable salts are all those which make available silver ions sufficiently rapidly under the reaction conditions, so that the reaction kinetics determined by the reaction procedure are not substantially influenced. AgNO 3 is the preferred silver salt because of the good commercial availability.
  • the silver salt can be added to the reaction in the form of a solution or directly as a solid.
  • a suitable solvent for the silver salt is, inter alia, the polyol employed in the reaction, that is to say preferably ethylene glycol and/or glycerol. The addition can take place all at once, in portions or continuously over a relatively long period of time.
  • the silver salt is added at the reaction temperature.
  • the silver salt is added in an amount which corresponds mathematically to a silver concentration of at least 0.5 wt. % in the reaction mixture. In preferred embodiments of the invention, silver is present in a concentration of at least 1.0 wt. %, more preferably of at least 2.5 wt. %, most preferably of at least 5.0 w
  • the organic chemical which is adsorbed on to the silver surface is required in the polyol process for formation of the desired wire-shaped morphology.
  • the scientific literature has been concerned with this phenomenon since the early 1990s. Different mechanisms and various tasks have been assigned to these chemicals in the past. They are said, inter alia, to prevent the agglomeration of the nanoparticles formed or to occupy specifically the metal lattice surfaces formed.
  • Such organic chemicals which are adsorbed on to the silver surface are known, for example, from WO 2009/128973 A2.
  • the organic chemical which is adsorbed on to the silver surface can be a liquid.
  • the chemical can be mixed directly with other reactants or it can be first diluted by mixing with a solvent or a mixture of solvents, which may contain a polyol.
  • the organic chemical which is adsorbed on to the silver surface can also be solid and is then first dissolved in a solvent, before it is mixed with the other reactants. It is not critical for the organic chemical which is adsorbed on to the silver surface to dissolve completely in the solvent; a suspension of the organic chemical which is adsorbed on to the silver surface can also be used.
  • the solvent can be a polyol or a mixture of a polyol and one or more other solvents.
  • the one or more other solvents can be chosen such that, either by themselves or as a mixture, they dissolve the organic chemical which is adsorbed on to the silver surface. No particular restriction exists for the solvent, as long as it does not impede or prevent the solution-mediated production of desired nanostructures, such as e.g. silver nanowires.
  • the organic chemical which is adsorbed on to the silver surface is usually chosen such that even at the reaction temperature it does not react to any substantial extent with the polyol or any other solvent.
  • Each solvent used for dissolving the organic chemical which is adsorbed on to the silver surface should likewise be chosen such that it does not impede or prevent the solution-mediated production of desired nanostructures, such as e.g. silver nanowires. If the reaction mixture at the reaction temperature comprises no other solvent for the organic chemical which is adsorbed on to the silver surface, the organic chemical which is adsorbed on to the silver surface should also dissolve in the polyol at least up to a certain degree.
  • the organic chemical which is adsorbed on to the silver surface can have, for example, a solubility at room temperature of at least about 1 g per litre of solvent (solvent mixtures being included), e.g. at least about 5 g per litre of solvent, at least about 10 g per litre of solvent or at least about 20 g per litre of solvent.
  • the organic chemical which is adsorbed on to the silver surface has a solubility of at least about 100 g per litre of solvent, e.g. at least about 200 g per litre of solvent or at least about 300 g per litre of solvent.
  • solutions of the organic chemical which is adsorbed on to the silver surface can be prepared in any concentration which is feasible and in which the desired nanostructures, such as e.g. silver nanowires, can be produced.
  • PVP polyvinylpyrrolidone
  • concentration is calculated using the monomer weight and not the average molecular weight of the polymer.
  • the molar concentration of PVP solution would be calculated e.g. by dividing the grams of PVP used for the preparation of one litre of the OPA solution by 111 g/mol and not by 55,000 g/mol.
  • the present invention also includes the joint use of two or more different organic chemicals which are adsorbed on to the silver surface.
  • a mixture of two or more different low molecular weight compounds or a mixture of two or more of the same or different polymers can be used, the polymers, if they are the same, being of different molecular weight.
  • a mixture of one or more compounds of low molecular weight and one or more polymers can be used.
  • the organic chemicals which are adsorbed on to the silver surface can be e.g. a mixture of polymers having a similar molecular weight (e.g. polyvinylpyrrolidone having an approximate molecular weight of 55,000).
  • the organic chemical which is adsorbed on to the silver surface can be a mixture which comprises one or more of these commercially available polymer mixtures.
  • the organic chemical which is adsorbed on to the silver surface can comprise e.g. polyvinylpyrrolidone having an average molecular weight of 55,000 and polyvinylpyrrolidone having an average molecular weight of 1,300,000.
  • the organic chemical which is adsorbed on to the silver surface can comprise a mixture of different polymers.
  • the organic chemical which is adsorbed on to the silver surface can comprise e.g. polyvinylpyrrolidone having an average molecular weight of 55,000 and polyvinyl alcohol having an average molecular weight of 35,000.
  • the organic chemical which is adsorbed on to the silver surface is a substance which is capable of interacting electronically with a metal atom of a nanoparticle.
  • a substance can comprise one or more atoms (e.g. at least two atoms) having one or more free electron pairs, such as e.g. oxygen, nitrogen and sulphur.
  • the organic chemical which is adsorbed on to the silver surface can be capable of a coordinative interaction with a metal atom on the surface of a nanoparticle and/or of chelating the metal atom.
  • the organic chemicals which are adsorbed on to the silver surface can comprise e.g. one or two O and/or N atoms.
  • the atoms having a free electron pair can be present in the substance in the form of a functional group, such as e.g. a hydroxyl group, a carbonyl group, an ether group and an amino group, or as a component of a functional group which comprises one or more of these groups as its structural element.
  • a functional group such as e.g. a hydroxyl group, a carbonyl group, an ether group and an amino group, or as a component of a functional group which comprises one or more of these groups as its structural element.
  • Non-limiting examples of suitable functional groups comprise —COO—, O—CO—O—, —CO—O—CO—, —C—O—C—, —CONR—, —NR—CO—O—, —NR 1 —CO—NR 2 —, —CO—NR—CO—, —SO 2 NR— and —SO 2 —O—, wherein R, R 1 and R 2 in each case independently represent hydrogen or an organic radical (e.g. an aliphatic or aromatic, unsubstituted or substituted radical which comprises from about 1 to about 20 carbon atoms).
  • Such functional groups can comprise the above (and other) structural elements as part of a cyclic structure (e.g.
  • the organic chemical which is adsorbed on to the silver surface is or comprises a substance which is capable of reducing the metal compound.
  • a specific, non-limiting example of such a substance is polyvinylpyrrolidone (PVP).
  • the organic chemical which is adsorbed on to the silver surface can have in total at least about 10 atoms per molecule which are chosen from C, N and O— e.g. at least about 20 such atoms or at least about 50 such atoms. In some embodiments, the organic chemical which is adsorbed on to the silver surface has in total at least about 100 C, N and O atoms per molecule: e.g. at least about 200, at least about 300 or at least about 400 C, N and O atoms per molecule. In the case of polymers, these figures relate to the average per polymer molecule.
  • the organic chemical which is adsorbed on to the silver surface can comprise an organic compound of low molecular weight no higher than about 500.
  • the organic protective agent can have a molecular weight of no higher than about 300.
  • the organic chemical which is adsorbed on to the silver surface can comprise an oligomeric or polymeric compound.
  • polyvinylpyrrolidone having an average molecular weight in the range of from about 10,000 to about 1,300,000 is particularly useful for a production of silver nanowires.
  • polyvinylpyrrolidone having an average molecular weight of 55,000 is chosen.
  • organic chemicals which are adsorbed on to the silver surface and can be used by themselves or as mixtures include polyvinylpyrrolidone, polyvinyl alcohol and surfactants, such as e.g. sodium dodecyl sulphate (SDS) laurylamine and hydroxypropylcellulose.
  • SDS sodium dodecyl sulphate
  • an organic chemical of low molecular weight which is adsorbed on to the silver surface include fatty acids, in particular fatty acids having at least about 8 carbon atoms.
  • Non-limiting examples of oligomers/polymers for use as the organic chemical which is adsorbed on to the silver surface include homo- and copolymers (including polymers such as e.g. random copolymers, block copolymers and graft copolymers) which comprise units of at least one monomer which comprises one or more O atoms and/or one or more N atoms.
  • a non-limiting class of such polymers for a use in the present invention is formed by polymers which comprise at least one monomer unit which comprises at least two atoms chosen from O and N atoms.
  • Corresponding monomer units can include, for example, at least one hydroxyl group, carbonyl groups, ether bonding group and/or amino group and/or one or more structural elements of the formula: —COO—, —O—CO—O—, —CO—O—CO—, —C—O—C—, —CONR—, —NR—CO—O—, —NR 1 —CO—NR 2 —, —CO—NR—CO—, —SO 2 NR— and —SO 2 —O—, wherein R, R 1 and R 2 in each case independently represent hydrogen or an organic radical (e.g. an aliphatic or aromatic, unsubstituted or substituted radical which comprises from about 1 to about 20 carbon atoms).
  • an organic radical e.g. an aliphatic or aromatic, unsubstituted or substituted radical which comprises from about 1 to about 20 carbon atoms.
  • This group of monomers includes e.g. acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid.
  • the monomers from group (a) can be used either in the form of the free carboxylic acids or in the partly or completely neutralized form.
  • neutralization it is possible to use e.g. alkali metal bases, alkaline earth metal bases, ammonia or amines, e.g. sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, methanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine;
  • N-vinyllactams such as e.g. N-vinylpyrrolidone, N-vinyl-2-piperidone and N-vinylcaprolactam;
  • vinyl acetal, vinyl butyral, vinyl alcohol and ethers and esters thereof such as e.g. vinyl acetate, vinyl propionate and methyl vinyl ether), allyl alcohol and ethers and esters thereof, N-vinylimidazole, N-vinyl-2-methylimidazoline and the hydroxystyrenes.
  • Corresponding polymers can also comprise additional monomer units, e.g. units derived from monomers without a functional group, and halogenated monomers, aromatic monomers etc.
  • additional monomer units e.g. units derived from monomers without a functional group, and halogenated monomers, aromatic monomers etc.
  • Non-limiting examples of such monomers include olefins, such as e.g. ethylene, propylene, the butenes, pentenes, hexenes, octenes, decenes and dodecenes, styrene, vinyl chloride, vinylidene chloride, tetrafluoroethylene etc.
  • the polymers for use in the process of the present invention as the organic chemical which is adsorbed on to the silver surface moreover are not limited to addition polymers, but also include other types of polymers, e.g. condensation polymers, such as e.g. polyesters, polyamides, polyurethanes and polyethers, as well as
  • polymers for a use in the present invention include polymers which comprise monomer units from one or more unsubstituted or substituted N-vinyllactams, such as e.g. those having from about 4 to about 8 ring members, e.g. N-vinylcaprolactam, N-vinyl-2-piperidone and N-vinylpyrrolidone. These polymers include homo- and copolymers. In the case of copolymers (which include e.g. random, block and graft copolymers), the N-vinyllactam (e.g. N-vinylpyrrolidone) units can be present in an amount of at least about 10 mol %, e.g.
  • the comonomers can include one or more of those mentioned in the preceding paragraphs, including monomers without a functional group (e.g. ethylene, propylene, styrene etc.), halogenated monomers etc.
  • substituents can include: alkyl groups (e.g. alkyl groups having from 1 to about 12 carbon atoms, e.g. from 1 to about 6 carbon atoms, such as e.g. methyl ethyl, propyl and butyl), alkoxy groups (e.g. alkoxy groups having from 1 to about 12 carbon atoms, e.g. from 1 to about 6 carbon atoms, such as e.g. methoxy, ethoxy, propoxy and butoxy), halogen atoms (e.g. F, Cl and Br), hydroxyl, carboxyl and amino groups (e.g. dialkylamino groups, such as e.g. dimethylamino and diethylamino) and any combinations of these substituents.
  • alkyl groups e.g. alkyl groups having from 1 to about 12 carbon atoms, e.g. from 1 to about 6 carbon atoms, such as e.g. methyl ethyl, prop
  • Non-limiting specific examples of vinyllactam polymers for use in the present invention include homo- and copolymers of vinylpyrrolidone.
  • these polymers can include:
  • (a) vinylpyrrolidone homopolymers such as e.g. classes K-15 and K-30 having K value ranges of 13-19 or 26-35, corresponding to average molecular weights of about 10,000 and about 67,000;
  • water-soluble polymers In the context of the present invention, the use of water-soluble polymers is preferred.
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • Suitable comonomers are e.g. N-vinylimidazole, vinyl acetate and vinylcaprolactam.
  • the organic chemicals which are adsorbed can be added to the reaction in the form of a solution or directly as a solid.
  • a suitable solvent for the chemicals is, inter alia, the polyol employed in the reaction, that is to say preferably ethylene glycol and/or glycerol.
  • the addition can take place all at once, in portions or continuously over a relatively long period of time.
  • the addition can take place before or during heating of the polyol or only when the reaction temperature is reached.
  • the concentration in the reaction mixture of the chemicals which are adsorbed may be matched to the addition of the silver salt.
  • concentrations of the chemicals which are adsorbed e.g. between 0.05 wt. % and 5 wt. % is carried out at the corresponding target concentration of silver salt and the morphology (length and diameter) and the yield of silver nanowires is determined. After evaluation of the experiments, the optimum concentration range is roughly demarcated.
  • the concentration of the chemicals which are adsorbed can be optimized still more precisely to the desired morphology and a high yield by means of a second series of experiments in which the concentrations are varied in a narrower range.
  • the preferred concentration range of the chemical which is adsorbed was determined as at least 0.05 wt. % from the experiments. Particularly preferably, the concentration is at least 0.2 wt. %, especially preferably at least 0.5 wt. % and very particularly preferably 1.0 wt. % in the reaction mixture.
  • halide ions can already be present as an unavoidable trace constituent in the other chemicals added, in particular in the solvent and in the organic chemical which is adsorbed on to metal surfaces, or can be added to the reaction mixture separately.
  • traces of halides in particular F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ .
  • anions from the group of pseudohalides in particular SCN ⁇ , CN ⁇ , OCN ⁇ , CNO ⁇
  • concentrations of the halides/pseudohalides to achieve high yields and favourable aspect ratios (length of the nanowires/diameter of the nanowires) may be matched to the particular recipe and the reaction conditions.
  • the influences on yield and morphology can be investigated by means of series of experiments with varying concentrations of halides and/or pseudohalides under otherwise constant reaction conditions.
  • the preferred concentration range of the halide/pseudohalide ion concentration was determined as 5 ppm to 2,000 ppm from the experiments. Particularly preferably, the concentration is in the range of from 20 ppm to 1,000 ppm and especially preferably in the range of from 50 ppm to 500 ppm in the reaction mixture.
  • Preferred chemicals for establishing the halide/pseudohalide ion concentration are the corresponding ammonium or alkali metal salts or the corresponding acids.
  • the use of NaCl, NaBr, NaI, NaSCN, KCl, KBr, KI and KSCN is particularly preferred.
  • the halide ions can be added by means of other substances which release halide ions.
  • Particularly preferred substances are the elemental halogens and the halogens in higher oxidation levels.
  • Particularly preferred substances are Br 2 , NaClO, I 2 , NaClO 3 , NaBrO 3 , NaIO 3 , KClO 3 , KBrO 3 and KIO 3 , in each case as a solid or in solution. Under the reaction conditions, the corresponding halide ions are at least partly formed from these substances.
  • the production of silver nanowires by the process according to one or more embodiments of the invention may benefit from the addition of a chemical which forms a redox pair, chosen from the group of Br ⁇ /Br 2 /BrO 3 ⁇ , I ⁇ /I 2 /IO 3 ⁇ , or V(0)/V(II)/V(III)/V(IV)/V(V).
  • a chemical which forms a redox pair chosen from the group of Br ⁇ /Br 2 /BrO 3 ⁇ , I ⁇ /I 2 /IO 3 ⁇ , or V(0)/V(II)/V(III)/V(IV)/V(V).
  • Fe(II)/Fe(III) for production of silver nanowires is known from the prior art. The role of iron is discussed in various ways in the literature. In US 2009/0282948 A1 Fe(II) is attributed the task of oxidizing molecular oxygen adsorbed on to the metal surface.
  • the Fe(III) thereby formed is reduced again to Fe(II) by the solvent/reducing agent.
  • the redox pair is automatically converted back into the reduced form by the reaction conditions, in particular by the reducing agent present in excess.
  • the chemical form in which the redox pair is added is unimportant.
  • the reduced form of the redox pair is formed from the “chemical which produces a redox pair”.
  • the addition of Fe(II) or Fe(III) can take place without an influence on the success of the synthesis.
  • halogens bromine and iodine can take over the role of the redox pair in the reaction.
  • Bromine and iodine can be added to the reaction in elemental form, as bromide or iodide or bromate or iodate.
  • a further halide/pseudohalide is employed, as a result of which particularly high yields are achieved.
  • Iodine is preferably added in the form of KI.
  • Bromine is preferably added in the form of KBr.
  • the concentration of chemicals which form redox pairs was determined as 5 ppm to 2,000 ppm from the experiments.
  • the concentration is in the range of from 20 ppm to 1,000 ppm and especially preferably in the range of from 50 ppm to 500 ppm in the reaction mixture.
  • the rate of reaction can be influenced by addition of alkali or acid.
  • the formation of the silver nanowires proceeds in competition with the formation of other ordered structures and irregular silver bodies. If the rates of reaction are too high, the content of irregular bodies increases.
  • acid By addition of acid, the rate of reaction can be matched to a degree suitable for the formation of silver nanowires.
  • many inorganic and also organic acids are suitable for addition in the processes according to the invention. Hydrogen halide acids, in particular HCl, HBr and HI, and nitric acid are preferably employed. The addition of the acid is to be matched to the particular recipe and the reaction conditions.
  • Preferred acid concentration ranges can be determined by means of series of experiments with varying addition of acid under otherwise constant reaction conditions.
  • the preferred concentration range of the acid was determined from the experiments as 0.01 wt. % to 2.0 wt. %, particularly preferably as 0.02 wt. % to 1.0 wt. % and especially preferably as 0.05 wt. % to 0.5 wt. % in the reaction mixture.
  • the processes are carried out at elevated temperatures of more than 100° C.
  • the studies by the inventors have shown that carrying out the processes according to the invention at temperatures above 145° C. gives significantly higher yields of silver nanowires than are achieved at reaction temperatures below 145° C.
  • the processes according to the invention are carried out at temperatures of between 145° C. and 200° C., further preferably between 150° C. and 180° C., particularly preferably between 155° C. and 170° C.
  • the halide/pseudohalide additions, the additions which form redox pairs and the additions which are adsorbed on to the metal surface can take place directly to the cold polyol, during the heating phase or to the hot polyol.
  • the silver salt is advantageously first added at the reaction temperature.
  • the silver salt and chemicals which are adsorbed can be added simultaneously, in direct succession, alternately in portions or simultaneously over a relatively long period of time.
  • the formation of the silver nanowires can be readily monitored visually when carrying out the process according to the invention.
  • a nacreous, iridescent dispersion is present.
  • the evolution of gas which occurs during the reaction ceases.
  • the reaction mixture is allowed to cool, while stirring.
  • the dispersion can be diluted with a suitable solvent.
  • Suitable solvents are, for example, alcohols, such as EtOH and isopropanol, or also water.
  • the silver nanowires which have been decanted off can be kneaded, extruded or stirred into polymers for further processing.
  • the silver nanowires produced by one of the abovementioned processes preferably have a length of from 1 ⁇ m to 200 ⁇ m, a diameter of from 50 nm to 1,300 nm and an aspect ratio (length/diameter) of at least 5.
  • the silver nanowires produced by the processes according to the invention can be used for numerous applications.
  • the silver nanowires are particularly advantageously employed where their unique physical, biological and chemical, in particular the electrical, electronic, heat-conducting, mechanical, optical, antimicrobial and catalytic properties can be advantageously utilized.
  • a preferred field of use for the silver nanowires is the field of electrically conductive layers or materials.
  • the effects resulting from the anisotropy of the particles, such as e.g. low percolation limit and high conductivity at a low filler content, can be advantageously utilized here.
  • Lacquer or polymer layers having a filler content of from about 1 vol. % of the silver nanowires according to the invention already show the electrical conductivity of a metallic conductor. Conductivity at such low filler contents is often accompanied by a high optical transparency of the materials and scarcely changed mechanical properties of the carrier systems.
  • inks and pastes optionally in a mixture with other conductive materials, such as e.g. silver micro- and/or silver nanoparticles and/or conductive carbon species (carbon nanotubes, carbon black, fullerenes, graphene, carbon fibres etc.) is particularly advantageous.
  • conductive materials such as e.g. silver micro- and/or silver nanoparticles and/or conductive carbon species (carbon nanotubes, carbon black, fullerenes, graphene, carbon fibres etc.) is particularly advantageous.
  • Such systems can be used inter alia in the field of printed strip conductors, for connection of thin layer systems or for the production of printable electronic components, such as e.g. capacitors or transistors.
  • the good electrical conductivity of systems containing silver nanowires renders possible the use thereof in the field of electric heating.
  • optically largely transparent, mechanically stable, interference pattern-free, heatable layers have been of technical interest for a long time.
  • all synthetic and natural polymers, thermoplastics and thermosets as well as dispersions are possible for the preparation of such conductive polymers.
  • Thermoplastic, synthetic polymers having a filler content of silver nanowire are suitable in particular.
  • the polymers preferably originate from the group of polyolefins (preferably polyethylene (PE), polypropylene (PP)), acrylonitrile/butadiene/styrene (ABS), from the group of polyamides (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), from the group of polyesters (e.g. polyethylene terephthalate (PET)), polystyrene (PS), polyether ketone (PEEK) and polyvinyl chloride (PVC).
  • Synthetic fibres having a filler content of silver nanowires are likewise particularly suitable for the production of heatable layers.
  • fibres of polyamide, polyester or of polypropylene are particularly preferred.
  • Films having a filler content of silver nanowires are furthermore particularly suitable for the production of heatable systems. Films of PET are particularly preferred.
  • Other outstandingly suitable systems for the production of heatable and optionally highly transparent layers are monomer solutions having a recipe with silver nanowires, such as e.g. monoalkyl acrylates or solutions of low molecular weight polymers, such as e.g. polyglycols, polyalcohols, polyketones and also technical grade lacquer resins.
  • the fibres can be made of thermoplastic polymers, corresponding to the above list of thermoplastics, or can also be natural fibres, such as cellulose, viscose, cotton, silk etc.
  • the electrically conductive fibres can likewise also be produced via electrospinning processes, and are thus produced from soluble amorphous and crystal-forming polymers, such as polyurethanes, co-polyesters, polyethylene oxide, polyvinyl alcohol, polyacrylonitrile, polyimide etc.
  • the electrically conductive fibres are then used in heating, sensor and data transfer applications which can be processed by textile technology.
  • silver nanowires produced according to the invention lie in the field of papermaking.
  • the silver nanowires according to the invention can thus be employed both as a filler in the paper pulp, as an additive in paper brush-on paints, and as a subsequent print or a coating deposited subsequently by chemical or physical means.
  • silver nanowires produced according to the invention are to be found inter alia in the fields of thermal conduction, thermally conductive pastes, thermally conductive adhesives, directional thermal conductivity, highly thermally conductive regions in high power LED and transistors and in thermogenerators.
  • the antimicrobial action of silver is the object both of current research and of industrial production. From a certain threshold concentration, the silver nanowires produced by the processes according to the invention can impart antimicrobial properties to correspondingly finished objects.
  • metal and in particular silver nanoparticles are suitable for use in surface plasmon resonance analysis (SPR analysis) and in surface enhanced Raman spectroscopy (SERS). Due to their geometric anisotropy, silver nanowires can be employed both individually and as an array for SPR analysis and for SERS and quite generally in the field of photonics.
  • the silver nanowires according to the invention can moreover be employed in optical filters.
  • the experimental procedure is analogous to that described in Example 1.
  • the reaction temperature is 155° C.
  • the reaction has ended after about 15 min.
  • the silver nanowires formed have a length of from 3 ⁇ m to 60 ⁇ m and a diameter of from 150 nm to 500 nm.
  • the yield of silver nanowires is 90% of the amount of silver employed.
  • the experimental procedure is analogous to that described in Example 1.
  • the reaction temperature is 130° C.
  • the reaction has ended after about 120 min.
  • the silver nanowires formed have a length of from 3 ⁇ m to 200 ⁇ m and a diameter of from 150 nm to 500 nm.
  • the coarse spherical silver particles formed alongside the silver nanowires cannot be separated off from the nanowires by means of sedimentation.
  • the yield of silver nanowires is estimated from the weight, incorporating the silver particles detected in the SEM photograph.
  • the yield of silver nanowires is about 25% of the amount of silver employed.
  • vanadium can likewise be employed in the processes according to the invention as an element which forms a redox pair.
  • the experimental procedure is analogous to that described in Example 1.
  • 6 mg of NaCl and no chemical which forms a redox pair (KI in Example 1) are added.
  • the reaction has ended after about 6 min.
  • the silver nanowires formed have a length of from 1 ⁇ m to 15 ⁇ m and a diameter of from 150 nm to 500 nm.
  • the coarse spherical silver particles formed alongside the silver nanowires cannot be separated off from the nanowires by means of sedimentation.
  • the yield of silver nanowires is estimated from the weight, incorporating the silver particles detected in the SEM photograph.
  • the yield of silver nanowires is about 50% of the amount of silver employed.
  • the experimental procedure is analogous to that described in Example 4. In deviation from Example 4, instead of NaCl, an amount of 9 mg of NaBr is added. The reaction has ended after about 6 min.
  • the silver nanowires formed have a length of from 3 ⁇ m to 35 ⁇ m and a diameter of from 150 nm to 500 nm. The yield of silver nanowires is 95% of the amount of silver employed.
  • the experimental procedure is analogous to that described in Example 4. In deviation from Example 4, instead of NaCl, an amount of 8 mg of KSCN is added. The reaction has ended after about 6 min.
  • the silver nanowires formed have a length of from 1 ⁇ m to 25 ⁇ m and a diameter of from 500 nm to 1,300 nm. The yield of silver nanowires is 85% of the amount of silver employed.
  • Example 7 the addition of chloride can be replaced by thiocyanate with low losses in the yield. It is striking that considerably thicker wires are formed by addition of thiocyanate compared with an addition of halide.
  • the reaction mixture is added to 150 ml of deionized water.
  • the supernatant is decanted off and dried.
  • the dried residue is investigated for its morphology by means of SEM. It consists practically exclusively of silver nanowires having a length of between 3 ⁇ m and 35 ⁇ m and a diameter of between 150 nm and 500 nm.
  • the yield of silver nanowires is 95% of the amount of silver employed.
  • Silver nanowires are produced according to Example 1.
  • 150 ml of ethanol and not 150 ml of water are added to the nanowire dispersion.
  • the supernatant is decanted off and discarded.
  • the sediment is stirred up again with 150 ml of ethanol and left to stand for sedimentation.
  • the supernatant is discarded.
  • the dry weight of the residue is determined as 70 wt. %.
  • 1.0 g of this ethanolic silver nanowire dispersion is added to 14 g of a lacquer base of 63 wt. % of 1-methoxy-2-propanol, 16 wt.
  • the lacquer obtained is drawn with a glass rod on to a glass carrier with a width of 30 mm.
  • the dried lacquer layer shows a surface resistance of 50 ohm.
  • the dry lacquer comprises approx. 31 wt. % of silver nanowires, which corresponds to about 4.1 vol. % of silver.

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* Cited by examiner, † Cited by third party
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US20110219913A1 (en) * 2008-11-18 2011-09-15 Kwang Suck Suh Method for manufacturing metallic nanowires using ionic liquids
US20140102255A1 (en) * 2012-10-16 2014-04-17 Niching Industrial Corporation Method of preparing silver nanowire
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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012102319A1 (de) 2012-03-20 2013-09-26 Rent A Scientist Gmbh Nichtlineare Nanodrähte
JP6266859B2 (ja) * 2012-05-07 2018-01-24 公立大学法人 滋賀県立大学 銀ナノワイヤの製造方法
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050056118A1 (en) * 2002-12-09 2005-03-17 Younan Xia Methods of nanostructure formation and shape selection
US20070056402A1 (en) * 2005-09-14 2007-03-15 Samsung Electro-Machanics Co. Ltd. Metal nanoparticles and method for manufacturing thereof
US20080003130A1 (en) * 2006-02-01 2008-01-03 University Of Washington Methods for production of silver nanostructures
US20090242231A1 (en) * 2008-03-31 2009-10-01 Fujifilm Corporation Silver nanowire, production method thereof, and aqueous dispersion
US20100078197A1 (en) * 2008-09-30 2010-04-01 Fujifilm Corporation Metal nanowires, method for producing the same, and transparent conductor
US7824466B2 (en) * 2005-01-14 2010-11-02 Cabot Corporation Production of metal nanoparticles
US20120297927A1 (en) * 2011-05-23 2012-11-29 Carestream Health, Inc. Branched nanowire preparation methods, compositions, and articles
US20120328469A1 (en) * 2011-06-24 2012-12-27 Carestream Health, Inc. Nanowire preparation methods, compositions, and articles
US20130126799A1 (en) * 2010-06-24 2013-05-23 Fujifilm Corporation Electroconductive film, touch panel and solar battery

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101333012B1 (ko) * 2005-08-12 2013-12-02 캄브리오스 테크놀로지즈 코포레이션 나노와이어 기반의 투명 도전체
CN101343529B (zh) * 2007-07-13 2010-09-01 中国科学院大连化学物理研究所 一种复合相变材料的制备方法
JP5570094B2 (ja) * 2007-11-12 2014-08-13 コニカミノルタ株式会社 金属ナノワイヤ、金属ナノワイヤの製造方法及び金属ナノワイヤを含む透明導電体
US7922787B2 (en) 2008-02-02 2011-04-12 Seashell Technology, Llc Methods for the production of silver nanowires
JP2009215573A (ja) * 2008-03-07 2009-09-24 Fujifilm Corp 棒状金属粒子及びその製造方法、並びに棒状金属粒子含有組成物、及び帯電防止材料
JP2009299162A (ja) 2008-06-16 2009-12-24 Fujifilm Corp 銀ナノワイヤー及びその製造方法、並びに水性分散物及び透明導電体
TW201131582A (en) * 2009-12-25 2011-09-16 Fujifilm Corp Conductive film, method for producing the same, and touch panel

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050056118A1 (en) * 2002-12-09 2005-03-17 Younan Xia Methods of nanostructure formation and shape selection
US7824466B2 (en) * 2005-01-14 2010-11-02 Cabot Corporation Production of metal nanoparticles
US20070056402A1 (en) * 2005-09-14 2007-03-15 Samsung Electro-Machanics Co. Ltd. Metal nanoparticles and method for manufacturing thereof
US20080003130A1 (en) * 2006-02-01 2008-01-03 University Of Washington Methods for production of silver nanostructures
US20090242231A1 (en) * 2008-03-31 2009-10-01 Fujifilm Corporation Silver nanowire, production method thereof, and aqueous dispersion
US20100078197A1 (en) * 2008-09-30 2010-04-01 Fujifilm Corporation Metal nanowires, method for producing the same, and transparent conductor
US20130126799A1 (en) * 2010-06-24 2013-05-23 Fujifilm Corporation Electroconductive film, touch panel and solar battery
US20120297927A1 (en) * 2011-05-23 2012-11-29 Carestream Health, Inc. Branched nanowire preparation methods, compositions, and articles
US20120328469A1 (en) * 2011-06-24 2012-12-27 Carestream Health, Inc. Nanowire preparation methods, compositions, and articles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Korte et al.; "Rapid Synthesis of Silver Nanowires through a CuCl- or CuCl2-mediated Polyol Process"; Journal of Materials Chemistry; Vol. 18, pp 437-441; 2008; no month available. *
Nandikonda et al.; "Effects of Salt Selection on the Rapid Synthesis of Silver Nanowires"; Abstract INOR-299; 240th ACS National Meeting; Boston Mass; 1 page; 8/2010. *

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9233421B2 (en) * 2008-11-18 2016-01-12 Kwang Suck Suh Method for manufacturing metallic nanowires using ionic liquids
US20110219913A1 (en) * 2008-11-18 2011-09-15 Kwang Suck Suh Method for manufacturing metallic nanowires using ionic liquids
US9606378B2 (en) 2012-02-16 2017-03-28 Commissariat A L'energie Atomique Et Aux Energies Alternatives Display screen and its manufacturing process
US20140102255A1 (en) * 2012-10-16 2014-04-17 Niching Industrial Corporation Method of preparing silver nanowire
US9079250B2 (en) * 2012-10-16 2015-07-14 Niching Industrial Corporation Method of preparing silver nanowire
US20150336173A1 (en) * 2012-12-14 2015-11-26 Inscon Tech Co., Ltd. Method for manufacturing silver nanowires using copolymer capping agents
US9349630B2 (en) * 2013-03-15 2016-05-24 Applied Materials, Inc. Methods and apparatus for electrostatic chuck repair and refurbishment
US20140268478A1 (en) * 2013-03-15 2014-09-18 Applied Materials, Inc. Methods and apparatus for electrostatic chuck repair and refurbishment
US10049908B2 (en) 2013-03-15 2018-08-14 Applied Materials, Inc. Methods and apparatus for electrostatic chuck repair and refurbishment
US10099291B2 (en) 2013-05-24 2018-10-16 Showa Denko K.K. Method for producing metal nanowires and silver nanowires
KR20160033713A (ko) * 2013-07-22 2016-03-28 헤레우스 도이칠란트 게엠베하 운트 코. 카게 은 나노와이어를 포함하는 패터닝 조성물
TWI645740B (zh) * 2013-07-22 2018-12-21 德商黑拉耶烏斯貴金屬公司 製造含銀奈米線組成物之層狀結構之方法
US20160162063A1 (en) * 2013-07-22 2016-06-09 Heraeus Deutschland GmbH & Co. KG Patterning of a composition comprising silver nanowires
US10983615B2 (en) 2013-07-22 2021-04-20 Heraeus Deutschland GmbH & Co. KG Patterning of a composition comprising silver nanowires
US10073549B2 (en) * 2013-07-22 2018-09-11 Heraeus Deutschland GmbH & Co. KG Patterning of a composition comprising silver nanowires
KR102253646B1 (ko) 2013-07-22 2021-05-20 헤레우스 도이칠란트 게엠베하 운트 코. 카게 은 나노와이어를 포함하는 패터닝 조성물
US9297074B2 (en) * 2013-12-31 2016-03-29 Shenzhen China Star Optoelectronics Technology Co., Ltd Liquid crystal display panel repairing method and repairing system
US20150184299A1 (en) * 2013-12-31 2015-07-02 Shenzhen China Star Optoeletronics Technology Co., Ltd. Liquid crystal display panel repairing method and repairing system
WO2015167133A1 (ko) * 2014-04-30 2015-11-05 서울대학교 산학협력단 표면개질된 은 나노와이어 및 이의 제조 방법
US10576546B2 (en) * 2014-05-20 2020-03-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Process for purifying metal nanowires
JP2017532431A (ja) * 2014-08-15 2017-11-02 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 導電性透明層の製造のための銀ナノワイヤーおよび結晶性セルロースの繊維を含む組成物
US10814898B2 (en) 2015-04-14 2020-10-27 Joyson Safety Systems Germany Gmbh Steering wheel assembly
US10376898B2 (en) 2015-06-12 2019-08-13 Dow Global Technologies Llc Method for manufacturing high aspect ratio silver nanowires
US10081020B2 (en) 2015-06-12 2018-09-25 Dow Global Technologies Llc Hydrothermal method for manufacturing filtered silver nanowires
CN105598463A (zh) * 2015-11-27 2016-05-25 深圳市乐普泰科技股份有限公司 银纳米粒子制备方法
US20170354374A1 (en) * 2016-06-13 2017-12-14 Verily Life Sciences Llc Ultra-Low Power One-Shot Hydration Sensing System
US10299723B2 (en) * 2016-06-13 2019-05-28 Verily Life Sciences Llc Ultra-low power one-shot hydration sensing system
CN106270551A (zh) * 2016-09-30 2017-01-04 天津宝兴威科技有限公司 一种长度为25μm纳米银线的合成方法
CN106475570A (zh) * 2016-09-30 2017-03-08 天津宝兴威科技有限公司 一种纳米银线的制造方法
US11478852B2 (en) * 2018-06-08 2022-10-25 Korea Institute Of Science And Technology Micro-nanostructure manufactured using amorphous nanostructure and manufacturing method therefor
US11511345B2 (en) * 2018-07-27 2022-11-29 Shenzhen Huake-Tek Co., Ltd. Method for preparing silver nano-rings
WO2020205900A1 (en) * 2019-04-03 2020-10-08 Cambrios Film Solutions Corporation Conductive nanostructure purification
CN113573827A (zh) * 2019-04-03 2021-10-29 英属维京群岛商天材创新材料科技股份有限公司 导电纳米结构的纯化
KR20220007598A (ko) * 2019-04-03 2022-01-18 캄브리오스 필름 솔루션스 코포레이션 전도성 나노구조체 정제
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CN114289728A (zh) * 2020-09-21 2022-04-08 湖北大学 一种银纳米线的合成与简单提纯方法
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