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WO2014073772A1 - Procédé de préparation de nanoparticules ayant une structure cœur-écorce et nanoparticules préparées ainsi - Google Patents

Procédé de préparation de nanoparticules ayant une structure cœur-écorce et nanoparticules préparées ainsi Download PDF

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Publication number
WO2014073772A1
WO2014073772A1 PCT/KR2013/006880 KR2013006880W WO2014073772A1 WO 2014073772 A1 WO2014073772 A1 WO 2014073772A1 KR 2013006880 W KR2013006880 W KR 2013006880W WO 2014073772 A1 WO2014073772 A1 WO 2014073772A1
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WIPO (PCT)
Prior art keywords
core
nanoparticles
metal
shell
particles
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Ceased
Application number
PCT/KR2013/006880
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English (en)
Korean (ko)
Inventor
김미영
유의현
임민기
박찬혁
연경열
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Lotte Fine Chemical Co Ltd
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Samsung Fine Chemicals Co Ltd
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Application filed by Samsung Fine Chemicals Co Ltd filed Critical Samsung Fine Chemicals Co Ltd
Publication of WO2014073772A1 publication Critical patent/WO2014073772A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units

Definitions

  • the present invention relates to a method for producing nanoparticles having a core-shell structure and to nanoparticles prepared therefrom.
  • TCEs Transparent Conductive Electrodes
  • ITO Indium Tin Oxide
  • the process temperature is high, it is fragile by external physical stimuli, and is vulnerable to bending deformation.
  • the film is broken when the substrate is bent when coated on a polymer substrate.
  • the price is gradually increasing, and a problem arises in the supply.
  • a flexible transparent electrode and attracting attention as a material that can replace ITO are conductive polymers, carbon nanotubes, graphene, and metal nanowires and nanoparticles.
  • carbon nanotubes or graphene have low conductivity and are difficult to improve permeability.
  • the metal nanowires represented by Ag nanowires are high in price and are expensive in the manufacture of transparent electrodes only with Ag nanowires, and the surface of the transparent electrodes is rough.
  • inkjet printing is difficult and high temperature process is impossible, and the process is limited and conductivity decreases with stretching.
  • the metal nanoparticles are prepared in the form of a conductive ink is used for electrode production by a process such as inkjet.
  • Such metal nanoparticles may include particles of gold, silver, platinum, copper, nickel, iron, cobalt, zinc, chromium, manganese and the like.
  • copper, nickel, iron, cobalt, zinc, chromium, manganese particles have a lower manufacturing cost than noble metal nanoparticles, but has a problem of low oxidation stability.
  • copper (Cu) has excellent conductivity with low price.
  • the conductivity is greatly reduced, so it is difficult to use as a conductive ink.
  • the conductivity may be reduced by the antioxidant used to prevent surface oxidation.
  • silver (Ag) which is mainly used as a nanoparticle of a conductive ink, is very expensive, and as the recent price skyrockets, there is an urgent need for an alternative material that is relatively inexpensive and has high electrical conductivity.
  • Core-shell structured nanoparticles have been proposed to prevent oxidation of the metal particles forming the core portion and to improve the electrical conductivity of the particles.
  • a typical one is a structure in which a shell layer is formed of silver (Ag) on the surface of core nanoparticles of copper (Cu).
  • the shell layer made of silver in the particles having such a structure prevents oxidation of copper in the core portion and improves electrical conductivity of the whole particle.
  • the conventionally used method for producing the core-shell structured nanoparticles is to reduce the precursor of the core particles with a reducing agent in a single phase, i.e., a single solvent, to produce core nanoparticles and form a shell layer for the particles.
  • the material was slowly added and reduced to form a shell layer on the surface thereof.
  • the problem with the method is that it is not easy to control the particle size of the nanoparticles formed when the reduction reaction in a single phase to prepare the core particles and the separation of the formed particles is not easy.
  • a salt solution of dilute silver (Ag) it is not easy to control the rate of addition of the solution. aggregation is often achieved.
  • the thickness of the shell layer formed is not easy to control.
  • the present invention provides a method for preparing nanoparticles having a core-shell structure at room temperature, particle size control, particle separation, and uniform production.
  • the present invention also provides a method of forming a shell layer which can control the thickness of the shell layer and does not cause aggregation of the shell layer forming material.
  • an object of the present invention is to provide nanoparticles that are prevented from oxidation, excellent in electrical conductivity, and advantageously economically.
  • the present invention provides a core-shell structured nanoparticle comprising a shell layer formed from a precursor represented by the following formula on the surface of a metal particle of the core:
  • X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23.
  • the core metal particles are copper, nickel, iron, cobalt, zinc, chromium or manganese particles.
  • the core metal particles are prepared from metal precursors having a structure represented by the following formula:
  • R is And R may be the same or different.
  • X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23).
  • the core metal particles are made from metal hexanoate.
  • the present invention provides a method for producing a core-shell structured nanoparticle, wherein the shell layer is formed by reducing a precursor represented by the following formula on the surface of the metal particle of the core:
  • X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23.
  • the metal particles of the core are prepared by reducing the metal hexanoate of the organic phase with a reducing agent of the aqueous phase.
  • the precursor is added dropwise to the metal particles of the core in the form of a solution containing a solvent in the organic phase.
  • the feed rate of the solution ranges from 1 ml / min to 30 ml / min.
  • the solution comprises an amine having an alkyl group of 4 to 18 carbon atoms.
  • the precursor is used in the range of 100 to 200 parts by weight based on the metal particles of the core.
  • the reduction reaction is controlled by distribution equilibrium in the organic phase (non-polar solvent) and the water phase (polar solvent), so that the particle size can be controlled and nanoparticles of the core having a uniform shape can be synthesized.
  • the thickness of the shell layer can be adjusted by controlling the reaction temperature and concentration by using the shell layer forming precursor which can control the redox reaction by high solubility and distribution equilibrium.
  • the core-shell structured nanoparticles prepared by the present invention are prevented from being oxidized by shelling core particles that are susceptible to oxidation and having high electrical conductivity, thereby preventing oxidation and improving electrical conductivity of the particles.
  • the present invention is advantageous in terms of economics compared to the case where the entire particle is provided by such particles by providing the particles containing the expensive metal only in the shell layer.
  • FIG. 1 illustrates a process of preparing core particles and forming a shell layer according to the manufacturing method of the present invention.
  • Figure 2 is a SEM photograph of the copper nanoparticles and Cu @ Ag particles prepared in the example.
  • Figure 3 is a SEM photograph of the particles produced in the comparative example.
  • the present invention is characterized in that it comprises a shell layer formed from a precursor represented by the following formula on the surface of metal particles of the core in order to improve its oxidation stability and improve electrical conductivity when preparing nanoparticles from highly oxidizable metals.
  • Core-shell structured nanoparticles are provided:
  • X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23.
  • metal precursor having a structure represented by the following formula can be used:
  • R is And R may be the same or different.
  • X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23).
  • the reaction solution is prepared by dissolving metal hexanoate in a solvent and a capping agent.
  • the capping agent participates in the reduction reaction of metal hexanoate and wraps around the formed nanoparticles to stabilize the particles.
  • the capping agent serves to prevent oxidation of the prepared metal nanoparticles. It also serves to control the particle size of the produced particles. Therefore, the capping agent preferably has a suitable chain length.
  • amine is used as an example as a capping agent. It is preferable that the said amine contains a C4-C18 alkyl group.
  • a capping agent may preferably be butyl amine (butylamine), octylamine (octylamine), dodecylamine (dodecylamine), oleyl amine (Oleylamine) and the like. More preferably, oleylamine is used as the capping agent.
  • Oleyl amine is an amine of oleic acid, a fatty acid, and because of its relatively high molecular weight, can be combined with metal nanoparticles to form a layer on the particle surface.
  • the oxidation stability of the metal nanoparticles can be increased by preventing external oxygen from diffusing into the core of the metal nanoparticles.
  • the oleamine amine combined with the metal nanoparticles may facilitate the dispersion of the nanoparticles in a solvent.
  • the metal hexanoate of the organic phase is reduced by a reducing agent of the aqueous phase.
  • the metal hexanoate migrates by distribution equilibrium between the organic phase and the aqueous phase and is reduced by the reducing agent present in the aqueous phase to be distributed and present in the aqueous and organic phases as shown in section 2.
  • a relatively low temperature preferably room temperature to 60 ° C.
  • particle size can be easily adjusted according to the type of capping agent to be used, and nanoparticles having a uniform form can be obtained.
  • the shell layer is formed by reducing the precursor represented by the following formula on the surface of the metal particles of the core thus formed:
  • X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23.
  • the precursor has high solubility in nonpolar solvents and is in equilibrium with the distribution between nonpolar and polar solvents. This is a means to prevent aggregation which has been a problem when compared to other conventional precursor materials that have been used to form shell layers on metal particle surfaces.
  • the precursor of the present invention administered to the metal particle surface is adsorbed only on the particle surface without forming agglomerates among them to form a shell layer. Accordingly, the present invention can provide a core-shell structure in which a uniform shell layer is formed on the surface.
  • the reaction temperature and the concentration of the precursor may be adjusted to form a shell layer having a desired thickness. Therefore, the core-shell structured particles of the present invention can control the thickness of the shell layer according to the reaction temperature and the precursor concentration. It is preferable to perform reaction temperature in the range of room temperature-40 degreeC, and to use a precursor in the range of 100-200 weight part with respect to the metal particle of a core. At low temperatures, the activity of the surface of the core particles decreases a lot and the reaction does not proceed. On the contrary, when the reaction temperature is higher than the above range, the reaction rate is so fast that aggregation of particles occurs and a uniform shell layer cannot be formed.
  • the precursor when used in an amount less than 100 parts by weight relative to the core particles, the precursor does not react with the surface of the core particles or forms a shell layer with a sufficient thickness to improve conductivity. There is a possibility that the viscosity of the solution rises so that a uniform shell layer is not formed over the entire surface of the core particles, and local aggregation occurs.
  • the core particles synthesized by the distribution equilibrium between the polar and nonpolar solvents are distributed in the polar and nonpolar phases as shown in FIG. 1.
  • the precursor solution on the nonpolar solvent is slowly added dropwise thereto to proceed with the reduction reaction.
  • the input rate of the precursor solution is preferably in the range of 1ml / min to 30ml / min. This is because if the feed rate is less than 1 ml / min, the reaction proceeds too slowly, and if the feed rate proceeds faster than 30 ml / min, the reduction reaction speeds up, which may cause aggregation.
  • the metal particles of the core act as a reducing agent on the precursor in the reaction in which the shell layer is formed. That is, even without a separate reducing agent, the metal particles directly reduce the precursor to form a shell layer on the surface thereof. Therefore, compared with the case of forming the shell layer from the reduction reaction by a separate reducing agent, the shell formation reaction in the present invention has the characteristics that the reaction rate is easily controlled and the bond between the core and the shell layer prepared therefrom is firm.
  • the precursor solution preferably includes an amine having an alkyl group having 4 to 18 carbon atoms.
  • an amine having an alkyl group having 4 to 18 carbon atoms examples, triethylamine, butylamine, octylamine, dodecylamine, oleylamine can be used.
  • the amines control the ionization of the precursor by the reaction equilibrium as follows.
  • the precursor forms a shell layer by redox reaction on the surface of the metal particles as described below in the ionized state, in which the amine acts as an anionic dopant as shown below.
  • the shell layer can be well formed from the precursor.
  • controlling the concentration of amines is one means of controlling the speed of the shell formation reaction and the thickness of the shell layer.
  • the precursor solution is preferably used by including the amine at a concentration of more than 0% by weight and 10% by weight or less.
  • the precursor represented by the above formula by controlling the concentration of the precursor solution, the reaction temperature, the feeding rate and the amount of the amine, it is possible to form a uniform shell layer with a desired thickness for the core particle surface.
  • the solution containing the copper nanoparticles was cooled to room temperature. Then 0.6 g of acetaldehyde (using a reagent of 85% purity) was added to quench the reduction reaction of the reducing agent. Next, the solution containing copper nanoparticles was installed in the thermostat set to 25 degreeC. Here, a solution of 150 parts by weight of silver 2-methylhexanoate and 0.1 parts by weight of triethylamine dissolved in 30 mL of xylene was slowly added dropwise at a rate of 10 ml / min. It was. The shell layer was then formed by standing for 1 hour at room temperature.
  • the copper nanoparticles of the core prepared according to the present invention had an average particle diameter of 100 nm, and it was confirmed that the shape was formed into a uniform spherical shape. In addition, the size of the particles increased as the Ag shell formed thereon.
  • the synthesized Cu @ Ag nanoparticles were prepared with 25 wt% of anhydrous octane ink and spin-coated on a glass substrate at a speed of 2000 rpm for 30 seconds. Heat treatment was performed at 300 ° C. for 15 minutes in an inert atmosphere (H 2 (5%) + Ar (95%)).
  • the film surface was photographed by Scanning Electron Microscope (SEM). 4, it can be seen that a coating film is formed in a state in which Ag is melted on the particles of the core. From this, it can be seen that the particles prepared in Examples form a shell layer on the surface of the core, and when the heat treatment is performed, the shell layer is melted to form a coating film.
  • This Ag coating film formed from the shell layer onto the core particles prevents oxidation of the core particles and exhibits excellent electrical conductivity.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention concerne des nanoparticules ayant une structure cœur-écorce comprenant une couche d'écorce formée à l'aide d'un précurseur représenté par la formule 1, et un procédé de préparation de celles-ci. Selon la présente invention, des nanoparticules de cœur, dont la dimension peut être régulée et qui ont une forme uniforme, peuvent être synthétisées par la régulation d'une réaction de réduction au moyen d'équilibre de partage dans une phase organique (solvant non polaire) et une phase aqueuse (solvant polaire). Ensuite, l'épaisseur de la couche d'écorce peut être régulée par la régulation d'une température de réaction et d'une concentration par l'utilisation du précurseur de formation de couche d'écorce qui permet la régulation d'une réaction d'oxydoréduction au moyen de solubilité élevée et d'équilibre de partage.
PCT/KR2013/006880 2012-11-07 2013-07-31 Procédé de préparation de nanoparticules ayant une structure cœur-écorce et nanoparticules préparées ainsi Ceased WO2014073772A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020120125316A KR20140058893A (ko) 2012-11-07 2012-11-07 코어-쉘 구조의 나노입자 제조 방법 및 그로부터 제조된 나노입자
KR10-2012-0125316 2012-11-07

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WO2014073772A1 true WO2014073772A1 (fr) 2014-05-15

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KR101898647B1 (ko) 2017-05-11 2018-09-14 서울과학기술대학교 산학협력단 은코팅 구리 호일을 이용한 접합 소재 및 이를 이용한 접합 방법
CN113600826A (zh) * 2021-07-27 2021-11-05 厦门大学 一种小尺寸Cu@Ag核壳纳米颗粒的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070058072A (ko) * 2005-12-01 2007-06-07 삼성전자주식회사 다층구조 나노결정의 제조방법
KR20070088086A (ko) * 2006-02-24 2007-08-29 삼성전기주식회사 코어-셀 구조의 금속 나노입자 및 이의 제조방법
KR100759715B1 (ko) * 2006-09-26 2007-10-04 고려대학교 산학협력단 균일한 크기의 복합기능 나노 입자 제조방법
KR20080107578A (ko) * 2007-06-07 2008-12-11 삼성전자주식회사 코어/쉘 나노결정 및 그 제조방법
KR20120116169A (ko) * 2011-04-12 2012-10-22 한국원자력연구원 산화안정성이 우수한 코어-쉘 구조의 금속 나노입자의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070058072A (ko) * 2005-12-01 2007-06-07 삼성전자주식회사 다층구조 나노결정의 제조방법
KR20070088086A (ko) * 2006-02-24 2007-08-29 삼성전기주식회사 코어-셀 구조의 금속 나노입자 및 이의 제조방법
KR100759715B1 (ko) * 2006-09-26 2007-10-04 고려대학교 산학협력단 균일한 크기의 복합기능 나노 입자 제조방법
KR20080107578A (ko) * 2007-06-07 2008-12-11 삼성전자주식회사 코어/쉘 나노결정 및 그 제조방법
KR20120116169A (ko) * 2011-04-12 2012-10-22 한국원자력연구원 산화안정성이 우수한 코어-쉘 구조의 금속 나노입자의 제조방법

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TW201422339A (zh) 2014-06-16

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