WO2016045648A1 - Procédé de préparation d'un mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection polymère, mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection polymère préparé par ce procédé, et formule d'impression qui contient ce mélange bimodal - Google Patents

Procédé de préparation d'un mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection polymère, mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection polymère préparé par ce procédé, et formule d'impression qui contient ce mélange bimodal Download PDF

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Publication number
WO2016045648A1
WO2016045648A1 PCT/CZ2015/000105 CZ2015000105W WO2016045648A1 WO 2016045648 A1 WO2016045648 A1 WO 2016045648A1 CZ 2015000105 W CZ2015000105 W CZ 2015000105W WO 2016045648 A1 WO2016045648 A1 WO 2016045648A1
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WO
WIPO (PCT)
Prior art keywords
copper
microparticles
mixture
protective layer
nanoparticles
Prior art date
Application number
PCT/CZ2015/000105
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English (en)
Inventor
Jan Macak
Tomas SYROVY
Tomas Wagner
Lubomir Kubac
Frantisek JOSEFIK
Original Assignee
Univerzita Pardubice
Centrum Organicke Chemie S.R.O.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Univerzita Pardubice, Centrum Organicke Chemie S.R.O. filed Critical Univerzita Pardubice
Priority to DE112015004362.4T priority Critical patent/DE112015004362T5/de
Publication of WO2016045648A1 publication Critical patent/WO2016045648A1/fr

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Classifications

    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • 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
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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 invention relates to a method for preparation of a bimodal mixture of copper nanoparticles and microparticles with a polymeric protective layer.
  • the invention also relates to a bimodal mixture of copper nanoparticles and microparticies with a polymeric protective layer prepared by this method and to a printing formulation containing this bimodal mixture.
  • Copper particles including nanoparticles and microparticles
  • silver and gold particles including nanoparticles and microparticles
  • copper particles are the most significant metallic particles which have found wide application, especially in electronics and catalysis, due to their excellent electrical conductivity, catalytic abilities and high chemical stability.
  • a large number of different methods have been developed for the preparation of copper particles having dimensions in the range from tens of nanometers to units of micrometers, some of the methods being more suitable, others less suitable.
  • the methods which are currently used also exhibit a number of disadvantages.
  • the most widely used methods for preparation of copper particles are based on liquid-step reduction, in which metallic copper is produced by reduction from a suitable precursor dissolved in a suitable solvent by using a suitable reducing agent.
  • the mean size of the particles thus prepared depends on the ratio of the copper precursor to the reducing agent, as well as on the specific reaction conditions (e.g. temperature, stirring conditions, order of mixing individual components together, addition of other agents, etc.).
  • SUBSTITUTE SHEETS commonly used copper precursor is copper sulfate, and also copper chloride, copper nitrate, copper acetylacetonate, copper acetate, cuprous oxide, cupric oxide , etc.
  • solvent systems are used, most often on the basis of water, organic solvents (e.g. acetone, toluene, etc.), alkanes (e.g. n-hexane, n-heptane, n-octane, etc.), ethylene glycol, polyethylene glycols or various mixtures thereof.
  • NaBH 4 sodium borohydrate
  • KH 4 potassium borohydrate
  • a reducing agent especially sodium borohydrate (NaBH 4 ) or potassium borohydrate (KBH 4 ) is used (see, e.g., the article by I. Lisiecki et al.: “Control of the shape and the size of copper metallic particles", Journal of the Physical Chemistry, 100 (1996) 4160, or H.-X. Zhang et al.: “Facile Fabrication of Ultrafine Copper Nanoparticles in Organic Solvent", Nanoscale Research Letters 4 (2009) 705), as well as hydrazine (see, e.g., the article by S.H.
  • reaction mixture often contains incorporated cations which are very difficult to remove, such as Na + , and which negatively affect the purity of the final product and its electrical conductivity.
  • these cations unfavourably contribute to a change in the surface potential of the produced copper nanoparticles and their excessive clustering, which complicates their further application.
  • the suitable chemically stable substance is, e.g., an organic substance, such as polymer, alken, etc., the advantage of which is the fact that after applying copper particles to the required substrate it can be removed by suitable treatment - most often by exposure to a temperature in the range from 200 to 400 °C, when the protective layer is decomposed by pyrolysis and the copper particles are electrically conductive interconnected.
  • the shortcoming of this method is that these temperatures are too high for some substrates to which copper nanoparticles are applied and which have recently found increasingly wide application in the sphere of printed electronics (e.g. thin polymeric films, fabrics, etc.).
  • removal of the protective layer is not always quantitative, and very often its residues or reaction products arising during its removal may lead to undesirable contamination of the layer of copper particles being formed.
  • the layer of copper particles created by printing is subsequently sintered by using sintering methods, thus producing a homogeneous compact layer with similar or the same uniform electrical conductivity throughout the layer's volume, which has been achieved so far only by standard methods of metal plating.
  • the advantage of printing is the fact that it enables continuous and high-speed application of specific patterns to different flexible as well as rigid substrates.
  • a number of methods which are based on power supply to the printed copper particles are used for the purpose of sintering, in order to cause their bulk melting or surface melting and their subsequent sintering. These methods include, e.g., hot air drying, exposure to infrared radiation, exposure to UV radiation, exposure to microwave radiation, photonic sintering - i.e.
  • the disadvantage of existing printing formulations containing only an addition of copper nanoparticles or microparticles is that in the first case they are not capable of forming a sufficiently strong and mechanically resistant layer, and in the second case the formed layer is highly porous and has uneven electrical conductivity.
  • the aim of the invention is to eliminate the disadvantages of the background art and propose a method for preparation of copper particles with a suitable distribution in size, and also to ensure protection of the copper particles from undesired surface oxidation by a layer of material which can be easily and quickly removed.
  • the aim of the invention is also these particles and a printing formulation which contains them.
  • the goal of the invention is achieved by a method for preparation of a bimoda! mixture of copper nanoparticles and microparticles with a polymeric protective layer, whose principle consists in that in the first step is prepared a reaction mixture containing at least one precursor of copper, an aqueous solution of at least one monohydric and/or polyhydric alcohol and at least one organic polymer in a weight ratio precursor (precursors) of copper : alcohol (alcohols) : organic polymer (polymers) 1 : 5-500 : 0.05-0.5, and in the second step at least one organic reducing agent is quantitatively added to this reaction mixture under intensive stirring, whereby the weight ratio precursor (precursors) of copper : organic reducing agent (agents) is 1 : 1-20.
  • This combination has a highly favourable influence on the electric conductivity of the layer formed, e.g., by printing or spraying the printing formulation which contains this mixture, since the nanoparticles fill the void spaces between the microparticies, thereby increasing the conductivity of the layer being created, or, in other words, they even out differences in its conductivity in the entire volume, reducing its resulting porosity and increasing its compactness.
  • the weight ratio precursor (precursors) of copper : alcohol (alcohols) : organic polymer (polymers) in the reaction mixture is 1 : 5-50 : 0,1-0,3 and/or the weight ratio precursor (precursors) of copper : organic reducing agent (agents) is 1 : 2-10.
  • Suitable precursors of copper include mainly copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, copper acetate, cuprous oxide, cupric oxide, whereby it is possible to use also any mixture of at least two of them.
  • a suitable alcohol is especially methanol, ethanol, propanol, butanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol, butandiol, glycerol, whereby it is possible to use also any mixture of at least two of them.
  • a suitable organic reducing agent is especially ascorbic acid, glucose, fructose, sucrose, acetaldehyde, dimethyl ketone, whereby it is possible to use also any mixture of at least two of them.
  • a suitable organic polymer is especially polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, arabic gum, xanthan gum, hydroxypropyl cellulose, acetyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, whereby it is possible to use also any mixture of at least two of them.
  • the goal of the invention is also achieved by bimodal mixture of copper nanoparticles and microparticies with a protective polymeric layer which is prepared by this method.
  • This mixture then contains a fraction of nanoparticles ranging in size from 1 to 200 nm and a fraction of microparticles ranging in size from 0.5 to 3 prn.
  • a printing formulation for printing electrically conductive layers whose principle consists in that it contains 55 to 85 % by weight, preferably 70 to 80 % by weight of the bimodal mixture of nanoparticles and microparticles with a protective polymeric layer.
  • Fig.1 is an image of a fraction of copper nanoparticles of a bimodal mixture of copper nanoparticles and microparticles prepared by the method according to the invention, taken by an electron microscope with 100,000x magnification
  • Fig. 2 is an image of a fraction of copper microparticles of a bimodal mixture of copper nanoparticles and microparticles prepared by the method according to the invention taken by an electron microscope with 5,000x magnification
  • Fig. 3. is an image of a layer of bimodal copper particles printed on a glass substrate, taken by an electron microscope with 650x magnification.
  • the method for preparation of copper particles with a polymeric protective layer and suitable distribution of their sizes according to the invention is based on the reduction of copper cations from at least one suitable copper precursor in an aqueous solution of at least one suitable monohydric and/or polyhydric alcohol by at least one suitable organic reducing agent, in the presence of at least one suitable organic polymer.
  • any common salt of copper can be used as a precursor of copper, such as copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, copper acetate, etc., or copper oxide, e.g., cuprous oxide, cupric oxide, etc., or possibly, a mixture of at least two of these precursors.
  • the alcohol used can be substantially any common monohydric alcohol, such as methanol, ethanol, propanol, butanol, isopropanol, etc., or any common polyhydric alcohol, such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, glycerol, etc., or any mixture containing at least two monohydric alcohols, or at least two polyhydric alcohols, or at least one monohydric and at least one polyhydric alcohol.
  • monohydric alcohol such as methanol, ethanol, propanol, butanol, isopropanol, etc.
  • any common polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, glycerol, etc., or any mixture containing at least two monohydric alcohols, or at least two polyhydric alcohols, or at least one monohydric and at least one polyhydric alcohol.
  • organic reducing agent e.g., ascorbic acid, glucose, fructose, sucrose, acetaldehyde, dimethyl ketone, etc., or any mixture of at least two of them.
  • the organic reducing agent is fed quantitatively to the reaction mixture, i.e. all the batch in the form of solid particles or an aqueous solution is added to it at a time, under very intensive stirring, which can be achieved by using a magnetic stirrer or reactor equipped with a mixing propeller (e.g. torax), whereby as a result of this procedure elementary copper is precipitated in the form of nanoparticles and microparticles, achieving a yield of up to 98 %.
  • a mixing propeller e.g. torax
  • organic polymer it is possible to use e.g. polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, arabic gum, xanthan gum, hydroxypropyl cellulose, acetyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, or any mixture of at least two of them.
  • This organic polymer/these organic polymers ensures/ensure better wettability of the resulting copper particles by the reaction mixture, which is advantageous for the rapid completion of the reaction, and at the same time - already during the reduction of elementary copper - forms a thin film on the surface of the resulting particles, whereby the film protects them from undesirable surface oxidation and prevents their agglomeration.
  • a reaction mixture is prepared, the reaction mixture containing at least one precursor of copper, an aqueous solution of at least one monohydric and/or at least one polyhydric alcohol as well as at least one organic polymer, whereby for diluting all these components the mixture is stirred at higher temperatures (at the speed of the stirrer below 200 mm).
  • the ratio (by weight) of the individual components of the reaction mixture precursor (precursors) of copper : alcohol (alcohols) : polymer (polymers) is 1 : 5-500 : 0.05-0.5; preferably 1 : 5-50 : 0.1-0.3.
  • the reaction mixture thus prepared is added at least one organic reducing agent under intensive stirring (at a speed of the stirrer of above 200 rpm, preferably, however, above 400 rpm) and the process of reduction and precipitation of copper particles is started, during which time the reaction mixture is still very intensively stirred.
  • the weight ratio of the precursor(s) of copper to the organic agent(s) is 1 : 1-20; preferably 1 : 2-10.
  • the separated mixture of copper nanoparticies and microparticles is washed with an organic solvent, e.g. isopropanol. After drying, this mixture is stored separately or in a solution, which prevents oxidation of copper nanoparticles and microparticles, e.g. in a solution of alcohol.
  • an organic solvent e.g. isopropanol.
  • the method for preparation of a mixture of copper nanoparticles and microparticles according to the invention is based on using basic, commonly available and therefore inexpensive chemicals, without unnecessary admixtures of cations and anions of parasitic elements, which results in very high yields (up to 98 %) at low manufacturing costs.
  • the result is always a bimodal mixture of copper nanoparticles and microparticles with a polymeric protective layer, i.e. a mixture whose particle size distribution curve has a bimodal character - this mixture contains both a fraction of copper nanoparticles having a diameter of approximately 1 to 200 nm (see Fig.
  • the main building blocks of the layer thus formed are copper microparticles, whereby the voids between them are filled up with copper nanoparticles, which even out the differences in the electrical conductivity of the formed layer throughout its entire volume, and at the same time reduce its final porosity and increase its compactness.
  • the best option is the use of the bimodal mixture of copper nanoparticles and microparticles in the form prepared by the method according to the invention; however, in case of need, it is possible to separate the individual fractions from each other and use them separately.
  • the mixture of nanoparticles and microparticles prepared by the method according to the invention is used for preparing a printing formulation (paste) for printing electrically conductive layers, whereby the content of the mixture of copper nanoparticles and microparticles therein is in the range from 55 to 85 %, preferably from 70 to 80% of the total weight of the printing formulation.
  • a printing formulation paste
  • the content of the mixture of copper nanoparticles and microparticles therein is in the range from 55 to 85 %, preferably from 70 to 80% of the total weight of the printing formulation.
  • standard components of currently used printing formulations see, e.g., examples 2, 3, 5 and 6 below
  • any of the known methods can be used for removing the organic polymer and for the sintering of the copper nanoparticles and microparticles, e.g. exposure to infrared radiation, exposure to UV radiation, exposure to microwave radiation, photonic sintering - i.e.
  • the result is a highly homogeneous layer of copper nanoparticles and microparticles having a thickness in the order of units to tens of pm, which exhibits a very low sheet resistance - as low as 0.02 ⁇ /m 2 - and which, unlike the layers formed using copper nanoparticles or microparticles prepared by known methods, does not require for achieving the desired mechanical rigidity an additional high temperature biscuit firing (above 300°C), which usually results in lowered conductivity of the prepared layers caused by the oxidation of copper, which is, of course, undesirable for their applications.
  • an additional high temperature biscuit firing above 300°C
  • Using a mixture of copper nanoparticles and microparticles prepared by the method according to the invention finally not only leads to reducing costs of the printing formulation preparation, but also to reducing costs of the production of the required conductive layers, as well as to lower demands for technology. Due to this, the bimodal mixture of copper nanoparticles and microparticles prepared by the method according to the invention, or the printing formulations which contain these mixtures, find application in electronics and electrical technology - everywhere, where there is a need for forming thin conductive layers, particularly in various printed electronic circuits and connections, radio frequency antennas, displays, sensors, etc.
  • the glass substrate with the applied printing formulation was sintered for 20 minutes at a temperature of 450 °C in an inert-atmosphere furnace, whereby a compact layer of copper nanoparticles and microparticles was formed from the printing formulation, the sheet resistance of the resulting layer measured by a four-point method being 0.04 ⁇ /m 2 .
  • the glass substrate with the applied printing formulation was sintered for 20 minutes at a temperature of 450 °C in an inert- atmosphere furnace, whereby from the printing formulation was formed a compact layer of copper nanoparttcles and microparticles, the sheet resistance of which measured by a four-point method was 0.034 ⁇ /m 2 .
  • Example 3
  • the glass substrate with the applied printing formulation was sintered for 20 minutes at a temperature of 450 °C in an inert- atmosphere furnace, whereby from the printing formulation was formed a compact layer of copper nanoparticies and microparticles, the sheet resistance of which measured by a four-point method was 0.038 ⁇ /m 2 .
  • the glass substrate with the applied printing formulation was sintered at a temperature of 450 °C in an inert-atmosphere furnace for 20 minutes, whereby from the printing formufation was formed a compact layer of copper nanoparticies and microparticles, the sheet resistance of which measured by a four-point method was 0.034 D/m 2 .

Abstract

L'invention concerne un procédé de préparation d'un mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection polymère. La première étape du procédé consiste à préparer un mélange de réaction qui contient au moins un précurseur de cuivre, une solution aqueuse composée d'au moins un alcool monohydrique et/ou polyhydrique et d'au moins un polymère organique selon un rapport en poids précurseur (précurseurs) de cuivre:alcool (alcools):polymère organique (polymères organiques) de 1:5-500:0,05-0,5, et la seconde étape consiste en ce qu'au moins un agent réducteur organique est quantitativement ajouté à ce mélange de réaction par agitation intense, le rapport en poids précurseur (précurseurs) de cuivre:agent réducteur organique (agents réducteurs organiques) étant de 1:1-20, moyennant quoi, à partir du mélange de réaction sous agitation intense constante, les nanoparticules et les microparticules de cuivre sont simultanément réduites et précipitées, lesquelles sont munies d'une couche de protection polymère organique (un mélange de polymères organiques). L'invention concerne également un mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection de polymère préparé à l'aide de ce procédé, et une formule d'impression destinée à imprimer des couches électroconductrices, qui contient 55 à 85 % en poids de ce mélange.
PCT/CZ2015/000105 2014-09-24 2015-09-14 Procédé de préparation d'un mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection polymère, mélange bimodal de nanoparticules et de microparticules de cuivre ayant une couche de protection polymère préparé par ce procédé, et formule d'impression qui contient ce mélange bimodal WO2016045648A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112015004362.4T DE112015004362T5 (de) 2014-09-24 2015-09-14 Verfahren zum Zubereiten eines bimodalen Gemischs aus Kupfer-Nanopartikeln und -Mikropartikeln mit einer polymeren Schutzschicht, bimodales Gemisch von Kupfer-Nanopartikeln und -Mikropartikeln mit einer polymeren Schutzschicht, zubereitet nach diesem Verfahren und eine Druckzubereitung, enthaltend dieses bimodale Gemisch

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZPV2014-653 2014-09-24
CZ2014-653A CZ307129B6 (cs) 2014-09-24 2014-09-24 Způsob přípravy bimodální směsi nanočástic a mikročástic mědi s polymerní ochrannou vrstvou

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WO2016045648A1 true WO2016045648A1 (fr) 2016-03-31

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CZ (1) CZ307129B6 (fr)
DE (1) DE112015004362T5 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110756823A (zh) * 2019-12-09 2020-02-07 成都市天甫金属粉体有限责任公司 一种球形纳米银粉的制备方法
CN111975011A (zh) * 2020-07-20 2020-11-24 华南理工大学 一种芯片无压烧结互连用纳米铜浆及其制备方法与应用

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080159902A1 (en) 2006-08-29 2008-07-03 Samsung Electro-Mechanics Co., Ltd. Method for manufacturing cubic copper or copper oxide nanoparticles
WO2009040479A1 (fr) 2007-09-28 2009-04-02 Oy Keskuslaboratorio - Centrallaboratorium Ab Nouvelles particules et leur procédé de fabrication
US20100009071A1 (en) * 2008-07-08 2010-01-14 Xerox Corporation Bimodal metal nanoparticle ink and applications therefor
DE102009015470A1 (de) * 2008-12-12 2010-06-17 Byk-Chemie Gmbh Verfahren zur Herstellung von Metallnanopartikeln und auf diese Weise erhaltene Metallnanopartikel und ihre Verwendung
WO2010100107A2 (fr) * 2009-03-02 2010-09-10 Colorobbia Italia S.P.A. Procédé de préparation de suspensions stables de nanoparticules de métal et suspensions colloïdales stables obtenues par ce biais
WO2010114769A1 (fr) 2009-03-31 2010-10-07 Applied Nanotech Holdings, Inc. Encre métallique
JP2010285678A (ja) * 2009-06-15 2010-12-24 Asahi Glass Co Ltd 銅複合粒子の製造方法、複合金属銅粒子の製造方法、銅ペーストおよび金属銅導体の製造方法
US20120251381A1 (en) 2009-07-30 2012-10-04 Lockheed Martin Corporation Articles containing copper nanoparticles and methods for production and use thereof
JP2013161544A (ja) * 2012-02-01 2013-08-19 Nano Cube Japan Co Ltd 導電性材料およびその製造方法
CN103341633A (zh) * 2013-06-24 2013-10-09 深圳先进技术研究院 一种导电油墨纳米铜的制备方法
US20140009545A1 (en) 2012-07-06 2014-01-09 Intrinsiq Materials Conductive ink formulas for improved inkjet delivery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101334601B1 (ko) * 2011-10-11 2013-11-29 한국과학기술연구원 고직선성의 금속 나노선, 이의 제조방법 및 이를 포함하는 투명 전도막

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080159902A1 (en) 2006-08-29 2008-07-03 Samsung Electro-Mechanics Co., Ltd. Method for manufacturing cubic copper or copper oxide nanoparticles
WO2009040479A1 (fr) 2007-09-28 2009-04-02 Oy Keskuslaboratorio - Centrallaboratorium Ab Nouvelles particules et leur procédé de fabrication
US20100009071A1 (en) * 2008-07-08 2010-01-14 Xerox Corporation Bimodal metal nanoparticle ink and applications therefor
DE102009015470A1 (de) * 2008-12-12 2010-06-17 Byk-Chemie Gmbh Verfahren zur Herstellung von Metallnanopartikeln und auf diese Weise erhaltene Metallnanopartikel und ihre Verwendung
WO2010100107A2 (fr) * 2009-03-02 2010-09-10 Colorobbia Italia S.P.A. Procédé de préparation de suspensions stables de nanoparticules de métal et suspensions colloïdales stables obtenues par ce biais
WO2010114769A1 (fr) 2009-03-31 2010-10-07 Applied Nanotech Holdings, Inc. Encre métallique
JP2010285678A (ja) * 2009-06-15 2010-12-24 Asahi Glass Co Ltd 銅複合粒子の製造方法、複合金属銅粒子の製造方法、銅ペーストおよび金属銅導体の製造方法
US20120251381A1 (en) 2009-07-30 2012-10-04 Lockheed Martin Corporation Articles containing copper nanoparticles and methods for production and use thereof
JP2013161544A (ja) * 2012-02-01 2013-08-19 Nano Cube Japan Co Ltd 導電性材料およびその製造方法
US20140009545A1 (en) 2012-07-06 2014-01-09 Intrinsiq Materials Conductive ink formulas for improved inkjet delivery
CN103341633A (zh) * 2013-06-24 2013-10-09 深圳先进技术研究院 一种导电油墨纳米铜的制备方法

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
A. SINHA ET AL.: "Preparation of copper powder by glycerol process", MATERIALS RESEARCH BULLETIN, vol. 37, 2002, pages 407
B. LEE ET AL.: "A low-cure-temperature copper nano ink for highly conductive printed electrodes", CURRENT APPLIED PHYSICS, vol. 9, 2009, pages E157 - E160
H.-X. ZHANG ET AL.: "Facile Fabrication of Ultrafine Copper Nanoparticles in Organic Solvent", NANOSCALE RESEARCH LETTERS, vol. 4, 2009, pages 705
I. LISIECKI ET AL.: "Control of the shape and the size of copper metallic particles", JOURNAL OF THE PHYSICAL CHEMISTRY, vol. 100, 1996, pages 4160
J. DING ET AL.: "Ultrafine Cu particles prepared by mechanochemical process", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 234, 1996, pages L1
S. JEONG ET AL.: "Controlling the Thickness of the Surface Oxide Layer on Cu Nanoparticles for the Fabrication of Conductive Structures by Ink-Jet Printing", AD. FUNCT. MATER, vol. 15, 2008, pages 679
S. MAGDASSI ET AL.: "Copper Nanoparticles for Printed Electronics: Routes Towards Achieving Oxidation Stability", MATERIALS, vol. 3, 2010, pages 4626 - 4638
S.H. WU ET AL.: "Synthesis of high-concentration Cu nanoparticles in aqueous CTAB solutions", JOURNAL OF COLLOIDAL INTERFACE SCIENCE, vol. 273, 2004, pages 165
W. YU ET AL.: "Synthesis and characterization of monodispersed copper colloids in polar solvents", NANOSCALE RESEARCH LETTERS, vol. 4, 2009, pages 465
Y. LEE ET AL.: "Large scale synthesis of copper nanoparticles by chemically controlled reduction of applications of inkjet-printed electronics", NANOTECHNOLOGY, vol. 19, 2008, pages 415604
Y. LEE ET AL.: "Large-scale synthesis of copper nanoparticles by chemically controlled reduction for applications of inkjet-printed electronics", NANOTECHNOLOGY, vol. 19, 2008, pages 415604

Cited By (3)

* Cited by examiner, † Cited by third party
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CN110756823A (zh) * 2019-12-09 2020-02-07 成都市天甫金属粉体有限责任公司 一种球形纳米银粉的制备方法
CN111975011A (zh) * 2020-07-20 2020-11-24 华南理工大学 一种芯片无压烧结互连用纳米铜浆及其制备方法与应用
CN111975011B (zh) * 2020-07-20 2022-01-18 华南理工大学 一种芯片无压烧结互连用纳米铜浆及其制备方法与应用

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