WO2019126884A1 - Procédé séquentiel pour la construction de nanoparticules de cuivre métallique, puis leur décoration ou revêtement avec des nanoparticules plus petites de métal secondaire - Google Patents

Procédé séquentiel pour la construction de nanoparticules de cuivre métallique, puis leur décoration ou revêtement avec des nanoparticules plus petites de métal secondaire Download PDF

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Publication number
WO2019126884A1
WO2019126884A1 PCT/CL2018/000042 CL2018000042W WO2019126884A1 WO 2019126884 A1 WO2019126884 A1 WO 2019126884A1 CL 2018000042 W CL2018000042 W CL 2018000042W WO 2019126884 A1 WO2019126884 A1 WO 2019126884A1
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acid
nanoparticles
derivatives
nps
reaction mixture
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PCT/CL2018/000042
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English (en)
Spanish (es)
Inventor
Harold Iván LOZANO ZARTO
Guillermo Antonio GONZALEZ MORAGA
Eglantina Javiera Benavente Espinosa
Fernando MENDIZABAL
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Universidad de Chile
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Universidad de Chile
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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
    • 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
    • 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
    • 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
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks

Definitions

  • the present invention relates to a process for obtaining copper nanoparticles (NPs), specifically with a size between 10 nm and 200 nm.
  • the state of the art does not propose a method of reducing the diffusion of copper in silicon by using a secondary metal that produces chemically stable bimetallic nanoparticles capable of blocking the copper path avoiding or delaying its diffusion, by a sequential method.
  • An object of the invention is a sequential method for the construction of decorated metallic copper nanoparticles (NPs), with a coating of smaller nanoparticles of the secondary metal, comprising: Dispersing in a hermetically sealed and oxygen-free container the amount of nanoparticles of copper in the working liquid medium, water, organic solvent, or solvent mixture, polar or apolar, necessary to reach a copper concentration in the range 0.00001 mg / mL - 1000 mg / mL, with an optimum of 6 mg / mL; Dissolve in a second container at least one stabilizing agent in an appropriate solvent until a molar concentration of 0.5 to 20 M is obtained; Mix the two solutions prepared in the previous steps in a reactor in oxygen-free atmosphere, with agitation in the range of 5 to 10,000 rpm for a homogenization time between 1 min and 24 hours; Add to the reaction mixture of the previous step a primary complexing agent in a molar concentration 5 to 12 M with agitation in the range of 5 to 10,000 rpm for
  • Figure 1 describes the method of the invention.
  • Figure 2 describes copper nanoparticles between 10 nm and 200 nm coated with secondary metal nanoparticles between 0.5-20 nm.
  • Figures 3 to 5 describe composition of the nanoparticles by atomic distribution maps of the elements present in some areas of the decorated nanoparticles.
  • Figures 6 to 8 describe suspensions stable to premature oxidation, as well as agglomeration, suitable for printing processes, according to the method of the invention.
  • Figures 9 and 10 describe the surface resistivity of the nanoparticles obtained with the method of the invention.
  • Figure 11 describes the degree of diffusion of copper from the composite nanoparticles obtained with the method of the invention.
  • Figure 12 describes the best behavior of one of the selected secondary metals, by the method of the invention. DESCRIPTION OF A PREFERRED EMBODIMENT
  • a method of reducing the diffusion of copper in silicon is proposed through the use of a secondary metal that produces chemically stable nanoparticles, capable of blocking the copper path, avoiding or delaying its diffusion.
  • the method is based on the manufacture of copper nanoparticles decorated with a metal of a specific group of metals that when applied on silicon and thanks to the sintering of CuNps, a diffusional barrier is created in situ.
  • silver is used for the collectors and, in the case of microprocessors, it is preferred to use aluminum for the interconnectors.
  • a diffusional barrier ⁇ 10nm
  • the materials used so far include nitrides (TiNX, SiCN, SiNX, TaNX, WNX, HfNX), carbides (SiCO, SiC), pure elements (Ta, Ru, Co, W, Ni) and alloys (RuW, TaSiN / Ti , CuMn, CuTi, CuZr, CuAL).
  • physical deposit techniques are used to create the diffusional barrier (PVD, CVD, PECVD, LPCVD, HFCVD, ALD, PEALD and sputtering).
  • the sequential method is the construction of metallic copper nanoparticles and their subsequent decoration or coating with smaller nanoparticles of the secondary metal.
  • Stage A Disperse in a hermetically sealed and oxygen-free container the amount of copper nanoparticles in the working liquid medium, water, organic solvent, or solvent mixture, polar or apolar, necessary to reach a copper concentration in the range 0.00001 mg / mL - 1000 mg / mL, with an optimum of 6 mg / mL.
  • Step B Dissolve in a second container at least one stabilizing agent in an appropriate solvent until a molar concentration of 0.5 to 20 M is reached, where the stabilizer which must be soluble and / or dispersible in the working liquid medium, can be selected among amphiphilic molecules, surfactants or polymers.
  • Amphiphilic molecules containing carboxyl, carbonyl, amino, amido, ammonium, thiol, hydroxyl, ketone, ester, ether, nitro, sulfonyl, phosphate, borate, halide or mixture thereof, with apolar groups such as aliphatic, aromatic or mixtures thereof .
  • Polymers such as poly (vinylpyrrolidone) (PVP), polyvinyl alcohol, polycarbonates, polyphenols, polyethylene glycol and polyols such as ethylene glycol, diethylene glycol, tri-ethylene glycol, propylene glycols, alkyldiols such as butanediols, dipropylene glycol and polyethylene glycols, chitosan and its derivatives, polyacids and derivatives thereof, mercaptoalkanoates, and oxybenzoic acids; herein, the polyacids including any one or more of those selected from a group of poly (acrylic acid), poly (maleic acid), poly (methyl methacrylate), poly (acrylic acid-co-methacrylic acid), poly (maleic acid- co-acrylic acid), and poly (acrylamide-co-coacrylic acid); cellulose acetates, polyvinylacetates, polysulfone, polyphenylsulphones, polyethersulfones, polyket
  • Step C Mix the two solutions prepared in stages A and B in a reactor in oxygen-free atmosphere, with agitation in the range of 5 to 10,000 rpm for a homogenization time between 1 min and 24 hours.
  • Step D Add to the reaction mixture of step C a primary complexer in a 5 to 12 M molar concentration with agitation in the range of 5 to 10,000 rpm for a time between 1 min and 24 hours, where the primary complexing agent is selected between mono-, bi- and / or tridentate chelating molecules; with givers, acceptors or both; inorganic such as ammonia (NH 3 ) and ammonium hydroxide, organic, or amphoteric; like those with carboxylic groups, thiols, hydroxyl, ketones, nitro, syphones, and / or halides such as carboxylic acids; primary and secondary amines: isopropylamine, butylamine, pentylamine, hexylamine heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecyl
  • Step E Add a pH regulator to the reaction mixture of step C, until the mixture is adjusted to a pH that increases the solvation of the secondary metal and it is in solution; where the regulator can be alkalis, acids or buffer solutions or pH buffer, weak or strong, or mixtures of them.
  • the regulator can be alkalis, sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), magnesium hydroxide (Mg (OH) 2 ), barium hydroxide (Ba (OH) 2 ) are selected, calcium hydroxide (Ca (OH) 2 ) including Arrhenius bases.
  • acids can be monoprotic or diprotic, organic or inorganic, but not limited to these.
  • Step F Add antifoam to the reaction mixture of step D in a concentration not greater than 1% of the total mixture and heat the reaction mixture between 10 and 120 ° C with agitation in the range of 5 to 10,000 rpm per a homogenization time between 1 min and 24 hours; wherein the antifoam is selected from high molecular weight alcohols such as hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1- pentadecanol, 1- hexadecanol, 1-heptadecanol, 1-octadecanol and any of these with branches in its main chain.
  • aromatics alcohols, and any defoamers for water-based systems are selected as antisugars based on polysiloxanes, based on mineral oil, based on vegetable oil, and based on polyure
  • Step G Add at least one ion source of the reductible secondary metal under stirring in the range of 5 to 10,000 rpm to the reaction mixture of step E which is in a 0.5 to 3 M molar concentration and maintain stirring in the range of 5 to 10,000 rpm of the reaction mixture for a time between 1 min and 24 hours; where the secondary metal is selected from at least one metallic element from the groups of III A to VA and from IB to VIII B of the periodic table of elements.
  • the secondary metal can be selected from the group: Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Hg, Ag, Au, Pd, Pt, Rh, Ir, Ru, Ta, Os, Sn, Sb, Ge , Ga, Se, Te, Cd, Si, Bi, In, Al, Re and / or Mo and mixtures, alloys and co-crystals of at least one of these elements.
  • Source ions of the secondary metal is selected from the salts of metals, metal oxides, hydroxides, hydroxides, or binary salts and organometallic species, ionic or covalent compounds, coordination compounds, hybrid composites and / or metal electrodes. It is possible to use all metal ion sources that are compatible in the context of this process and particularly that they are soluble or dispersible in the liquid reaction medium.
  • Step H Set the temperature of the reaction mixture of step E between -10 ° C to 120 ° C, depending on the metal, the additives and the liquid reaction medium.
  • Step I Add in agitation in the range of 5 to 10,000 rpm at least one reducer to the reaction mixture of stage H which is in a molar concentration between 0.5 and 3 M and maintain agitation in the range of 5 to 10,000 rpm of the reaction mixture for a time between 1 min and 24 hours; wherein the reductant is selected from hydrazine monohydrate and derivatives, hydroxylamine and its derivatives, monohydric alcohols such as methanol, ethanol, aldehyde such as formaldehyde, ammonium formate, acetaldehyde and propanoaldehyde or salts thereof, hypophosphites, sulfites, tetrahydroborates, lithium tetraaluminohydride.
  • the reductant is selected from hydrazine monohydrate and derivatives, hydroxylamine and its derivatives, monohydric alcohols such as methanol, ethanol, aldehyde such as formaldehyde, ammonium formate, acetalde
  • LiAIH 4 sodium borohydride
  • polyhydroxybenzene such as hydroquinone and its derivatives, phenylenediamines and their derivatives, aminophenols and their derivatives, carboxylic acids and their derivatives such as ascorbic acid, citric acid, but not limited thereto.
  • Step J Stop the reaction of step I by cooling to a temperature between 0 ° C-25 ° C keeping the agitation in the range of 5 to 10,000 rpm.
  • Step K Addition of at least one secondary complex pre-dissolved in the liquid reaction medium in a molar concentration between 0.1 and 1.5 M to the reaction mixture of stage I, where the secondary complexer is selected from chelating molecules mono-, bi- and / or tridentate; with givers, acceptors or both; inorganic, organic, or amphoteric; as those with carboxylic, aminos, thiols, hydroxyl, ketonic, nitro, sulfonic, and / or halide groups such as carboxylic acids and their derivatives, dicarboxylic acids, unsaturated carboxylic acids, ammonia (NH.), ammonium hydroxide, primary and secondary amines .
  • the secondary complexer is selected from chelating molecules mono-, bi- and / or tridentate; with givers, acceptors or both; inorganic, organic, or amphoteric; as those with carboxylic, aminos, thiols, hydroxyl, ketonic, nitro, sulf
  • the carboxylic acids and their derivatives are selected from the group ascorbic acid, citric acid, aliphatic and aromatic carboxylic acids, such as benzoic acid, phenylacetic acid, but not limited thereto.
  • dicarboxylic acids ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonadioic acid, decadioic acid, butenedioic acid, italic acid, 2,4-diphenylcyclobutan-1,3 acid - dicarboxylic acid, 3,4- diphenylcyclobutane-1,2-dicarboxylic acid, but not limited thereto.
  • the secondary complexing agent can be selected from unsaturated carboxylic acids: acrylic, crotonic, isocrotonic, sorbic, palmitoleic, sapienic, oleic, elaidic, vaccenic, linoleic, linoelaidic, citric acid, tartaric acid, cinnamic acid, without limiting them.
  • the primary and secondary amines are selected from, but not limited to: isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine.
  • Step L Add at least one antioxidant pre-dissolved in liquid reaction medium with a molar concentration between 0.5 and 3 M in the reaction mixture of step J; wherein the antioxidant is selected from carboxylic acids and their derivatives such as ascorbic acid, citric acid, hydrazine monohydrate and derivatives, hydroxylamine and its derivatives, monohydric alcohols such as methanol, ethanol, aldehydes such as formaldehyde, ammonium formate, acetaldehyde and propanoaldehyde or salts of these, hypophosphites and similar antioxidant agents.
  • carboxylic acids and their derivatives such as ascorbic acid, citric acid, hydrazine monohydrate and derivatives, hydroxylamine and its derivatives, monohydric alcohols such as methanol, ethanol, aldehydes such as formaldehyde, ammonium formate, acetaldehyde and propanoaldehyde or salts of these, hypophosphites and similar antioxidant agents.
  • Step M Ripen the mixture of stage L for a time of 1 min to 15 days, at a temperature between 10 ° C and 70 ° C with or without agitation in the range of 5 to 10,000 rpm.
  • Step N Wash the nanoparticles by centrifugation and / or dialysis with at least one solvent selected from water, preferably deionized, monoprotic solvents such as methanol, ethanol, isopropanol, acetone, low-boiling apolar solvents or a mixture of these, but not limited to these.
  • monoprotic solvents such as methanol, ethanol, isopropanol, acetone, low-boiling apolar solvents or a mixture of these, but not limited to these.
  • the size of the nanoparticles can be regulated by varying the molar ratio between the copper source, the polymer, the reaction temperature, the pH of the solution, the liquid reaction medium and the concentration and amount of the secondary metal.
  • inks are prepared in a matrix based on ethylene glycol and water with other stabilizers and compatibilizers with nanoparticulate contents of up to 50% w / w based on the matrix.
  • those nanoparticles can be used in the form of dispersions in water or in polar solvents of known concentration or in dry powder form.
  • amphiphilic molecules surfactants
  • polymers such as PVP or chitosan
  • at least one metallic element is selected from the groups of III A to VA and from IB to VIII B of the periodic table of elements.
  • the secondary metal can be selected from the group: Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Hg, Ag, Au, Pd, Pt, Rh, Ir, Ru, Ta, Os, Sn, Sb, Ge, Ga, Se, Te, Cd, Si, Bi, In, Al, Re and / or Mo and mixtures, alloys and co-crystals of at least one of these elements.
  • the ion source of the secondary metal is selected from the salts of metals, metal oxides, hydroxides, hydroxides, or binary salts and organometallic species, ionic or covalent compounds, coordination compounds, hybrid composites and / or metal electrodes, among others.
  • alkali metal hydrides As reducing agents, alkali metal hydrides, hydrazine, ascorbic acid, etc. can be used.
  • ascorbic acid Ascorbic acid, sodium citrate and small donor molecules can be used.
  • antioxidants we use ascorbic acid, sodium citrate and small donor molecules.
  • the solution acquires a blackish color that turns slowly to reddish black until reaching a dark burgundy red color with controlled release of foam on the surface.
  • the mixture matures for 30 minutes.
  • the reaction is stopped by the addition of 0.8806 g of pre-dissolved ascorbic acid in 5 mL of distilled water and 1.4705 g of pre-dissolved sodium citrate in 5 mL of distilled water. Magnetic stirring is maintained for 1 hour at room temperature.
  • the nanoparticles can be separated and washed by centrifugation with an aqueous solution of 1% ascorbic acid.
  • the metal distribution of decorated nanoparticles depends mainly on the synthesis method, but also on the nature of the metal.
  • the sequential method causes coating of the copper nanoparticles by those of the secondary metal, as shown in Figures 3 to 5.
  • Decorated nanoparticle inks The regulation of the synthesis conditions of the decorated nanoparticles, particularly the ripening time, allows to obtain stable suspensions to the premature oxidation, as well as to the agglomeration, with metal concentrations (between 5 and 50%) suitable for printing processes.
  • the products of the described preparations separated by centrifugation and re-dispersed in water or suitable solvents have sizes in the range 10-70 nm and optimal surface charge for injection printing or other type of deposition, as shown in figures 6 to 8 .
  • decorated nanoparticle inks (30-40% m / m) are prepared.
  • the substrate, silicon is cleaned by the RCA method, also removing the SiO 2 layer.
  • the application of the ink on the clean substrate is done by forming a thin layer of the suspension using the spin coating technique, ie dispersion by rotation at high speed (2000 rpm). The process is repeated several times until homogenous and reproducible layers are obtained.
  • the conductivity measurements glass is used instead of silicon.
  • the determination of the degree of diffusion of copper from the decorated nanoparticles is carried out by means of the direct determination of the profile of the copper concentration in the silicon. Analytical techniques of the highest degree of available sensitivity are used; that is, spectroscopy of photoelectrons emitted by X-rays (XPS) and X-ray microanalysis (EDS).
  • XPS X-ray photoelelectrons emitted by X-rays
  • EDS X-ray microanalysis
  • the XPS analyzes shown in Figure 1 1, show that under conditions of thermal stress (800 ° C) copper diffuses into silicon, regardless of the secondary metal (M1-M3) used, diffuses towards silicon, although in different proportions. However, that temperature far exceeds those usually used in applications, for example, those used in the field of solar cells (maximum 300 ° C). In fact, experiments performed with a lower heating ramp show the best behavior of one of the selected secondary metals, as shown in figure 12. This method also shows that there is a process of prior segregation of the secondary metal that leads to the formation of a barrier that decreases the diffusion of copper in silicon.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

L'invention concerne un procédé d'obtention de nanoparticules (NP) de cuivre, notamment d'une taille comprise entre 10 nm et 50 nm. Plus particulièrement, l'invention concerne un procédé pour la construction de NP de cuivre métallique, puis leur décoration ou revêtement avec des nanoparticules plus petites de métal secondaire. Les technologies existantes pour cellules solaires à base de silicium utilisent de l'argent mais jamais du cuivre étant donné que sa pénétration dans le substrat réduit considérablement l'efficacité du dispositif. Pour les interconnexions électriques dans des microprocesseurs, d'autres métaux sont utilisés, notamment de l'aluminium, malgré sa moindre conductivité électrique. Compte tenu du coût relativement élevé de l'argent, le remplacement de l'argent par du cuivre est économiquement intéressant, en particulier si ce dernier permet également d'utiliser des technologies d'impression par jet d'encre.
PCT/CL2018/000042 2017-12-29 2018-12-20 Procédé séquentiel pour la construction de nanoparticules de cuivre métallique, puis leur décoration ou revêtement avec des nanoparticules plus petites de métal secondaire Ceased WO2019126884A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CL3489-2017 2017-12-29
CL2017003489A CL2017003489A1 (es) 2017-12-29 2017-12-29 Método secuencial para la construcción de nanopartículas de cobre metálico y su posterior decoración o revestimiento con nanopartículas más pequeñas del metal secundario

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110278497A1 (en) * 2010-05-11 2011-11-17 China Medical University Nanometal dispersion and method for preparing the same
US20120091401A1 (en) * 2010-10-14 2012-04-19 Toshiba Tec Kabushiki Kaisha Metal nanoparticle dispersion
US8597397B2 (en) * 2005-01-14 2013-12-03 Cabot Corporation Production of metal nanoparticles
EP2810714A1 (fr) * 2012-05-11 2014-12-10 LG Chem, Ltd. Procédé de préparation de particule c ur-écorce soutenue par un support, et particule c ur-écorce soutenue par un support préparée par ce proédé
US9221044B2 (en) * 2012-06-13 2015-12-29 Uniwersytet Warszawski Flow system method for preparing substantially pure nanoparticles, nanoparticles obtained by this method and use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8597397B2 (en) * 2005-01-14 2013-12-03 Cabot Corporation Production of metal nanoparticles
US20110278497A1 (en) * 2010-05-11 2011-11-17 China Medical University Nanometal dispersion and method for preparing the same
US20120091401A1 (en) * 2010-10-14 2012-04-19 Toshiba Tec Kabushiki Kaisha Metal nanoparticle dispersion
EP2810714A1 (fr) * 2012-05-11 2014-12-10 LG Chem, Ltd. Procédé de préparation de particule c ur-écorce soutenue par un support, et particule c ur-écorce soutenue par un support préparée par ce proédé
US9221044B2 (en) * 2012-06-13 2015-12-29 Uniwersytet Warszawski Flow system method for preparing substantially pure nanoparticles, nanoparticles obtained by this method and use thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
NADAGOUDA, M.N ET AL.: "A Greener Synthesis of Core (Fe, Cu)-Shell (Au, Pt, Pd, and Ag) Nanocrystals Using Aqueous Vitamin C", CRYST. GROWTH DES., vol. 7, no. 12, 2007, pages 2582 - 2587, XP055622736 *
ZHOU, G ET AL.: "Aqueous Synthesis of Copper Nanocubes and Bimetallic Copper/Palladium Core-Shell Nanostructures", LANGMUIR, vol. 22, no. 13, 2006, pages 5900 - 5903, XP055622737 *

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