WO2009040479A1 - Novel particles and method of producing the same - Google Patents

Novel particles and method of producing the same Download PDF

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Publication number
WO2009040479A1
WO2009040479A1 PCT/FI2008/050543 FI2008050543W WO2009040479A1 WO 2009040479 A1 WO2009040479 A1 WO 2009040479A1 FI 2008050543 W FI2008050543 W FI 2008050543W WO 2009040479 A1 WO2009040479 A1 WO 2009040479A1
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Prior art keywords
nanoparticles
copper
group
metal
stands
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Application number
PCT/FI2008/050543
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English (en)
French (fr)
Inventor
Juha Maijala
Juha Merta
Jun Shan
Heikki Tenhu
Original Assignee
Oy Keskuslaboratorio - Centrallaboratorium Ab
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Application filed by Oy Keskuslaboratorio - Centrallaboratorium Ab filed Critical Oy Keskuslaboratorio - Centrallaboratorium Ab
Publication of WO2009040479A1 publication Critical patent/WO2009040479A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/20—Methods for preparing sulfides or polysulfides, in general
    • 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
    • B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure
    • C22C2200/02—Amorphous
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure
    • C22C2200/04—Nanocrystalline

Definitions

  • the present invention relates to novel nanoparticles and to the manufacture thereof.
  • the present invention concerns novel metal nanoparticles in which the metal is protected with organic ligands or groups.
  • the invention also discloses methods of producing such particles and to uses of the new metal nanoparticles.
  • Metallic nanoparticles such as gold, silver, and copper, have attracted extensive scientific and industrial interest due to their unique electronic, optical, and catalytic properties. They are the most promising nanomaterials and play an important role in fabrication of nanodevices as a result of their high electrical conductivity and chemical inertness.
  • copper Being less expensive than gold and silver, copper is a more attractive metal than these for use on an industrial scale and is interesting in nanoscience and nanotechnology because of its superior electrical conductivity and high cost performance. Attempts to chemically synthesize copper nanoparticles have been inadequate so far. The main reason is that copper is very prone to be oxidized on the nanoscale. Thus, for avoiding oxidation copper nanocrystals have been synthesized by chemical reduction in reverse micelles, the size and shape of copper nanocrystals being controlled by hydration of the reactants, the dynamic character of the micelles, surfactant, and the reducing agent concentration.
  • HDEHP bis(ethylhexyl)hydrogen phosphate
  • sugar glucose xanthates
  • PVP poly(N-vinyl-2-pyrrolidone)
  • PAMAM poly(amidoamine)
  • PPI poly(propylene imine)
  • the present invention is based on the idea of providing nanoparticles with a core of a suitable conductive metal, such as copper, said nanoparticles having an average particle size of, generally about 1 to 10 nm, and comprising at least one protective group or ligand bonded to the metal particles.
  • the protective group is derived from a thiol.
  • the novel nanoparticles are amorphous or nanocrystalline and exhibit interesting properties.
  • the present invention also provides a method of producing nanoparticles having an average particle size of about 1 to 10 nm, comprising the step of reducing, in the presence of a reducing agent, dithioester monomers to the corresponding thiols while simultaneously reducing a copper precursor to the corresponding metal to yield amorphous or nanocrystalline metal nanoparticles.
  • reaction step and the step of recovering the product are advantageously carried out in an atmosphere which is essentially free from oxygen to protect the metal particles to which the organic ligands are bonded from oxidation during the preparation.
  • novel nanoparticles can be used, e.g., for producing conductive and semiconductive structures and components.
  • the metal particle core is well protected against oxidation and the novel metal nanoparticles can be stored for extended periods of time.
  • the present nanoparticles in particular copper nanoparticles, larger crystalline agglomerates can be formed.
  • the nanoparticles as such are semiconductive and they can be used for producing semiconductive or conductive thin layers on a substrate for example by printing technologies or lithography.
  • Figure 1 shows the FTIR spectra of the starting material of 4-Cyanopentanoic acid dithiobenzoate (CPAD) and the as-prepared CuNPs;
  • Figure 2 shows the 1 H and 13 C NMR spectra of the as-prepared CuNPs;
  • Figure 3 shows TGA curves of CuNPs-I and -2;
  • Figures 4a to 4d show HRTEM images, EDS spectra and SAED patterns (inset) of CuNP-I (top row) and CuNP -2 (bottom row);
  • Figures 5a and 5b shows in situ WAXS heating measurements of both CuNPs from 30 0 C up to ca. 240 0 C under helium flow; the numbers on the right hand side are temperatures in Celsius; and Figure 6 shows the WAXS pattersn for hexagonal Cu 2 S phases of CuNP-I at moderate temperatures and the theoretical positions (dotted line) and intensities (solid line) of the reflections from hexagonal Cu 2 S (JCPDS 26-1116).
  • novel nanoparticles having a core of a metal surrounded by protective organic ligands are provided along with a method of preparing such nanoparticles using as a starting material a monomeric thiol.
  • the protective group bonded to metal is derived from a monomeric thiol having the formula I
  • R 1 stands for a cyclic group and R 2 stands for a bivalent group.
  • R 1 preferably stands for a cyclic group selected from aromatic and aliphatic groups.
  • the cyclic aromatic group is preferabl a benzyl or phenyl which optionally bears 1 to 5 substituents on the ring, or naphthyl, which optionally bear 1 to 11 substituents on the ring structure.
  • the bivalent group R 2 is, for example, a linear or branched aliphatic group selected from alkylene, alkenylene and alkynylene which optionally bears 1 to 3 substitutents.
  • the substitutents are preferably selected from the group of halogen, alkyl and alkenyl.
  • Halogen preferably designates chloro, bromo or iodo.
  • Alkyl stands for a hydrocarbon radical containing preferably 1 to 18, more preferably 1 to 14 and in particular preferred 1 to 12 carbon atoms.
  • the alkyl can be linear or branched.
  • the alkyl group is a lower alkyl containing 1 to 6 carbon atoms, which optionally bears 1 to 3 substituents selected from methyl and halogen.
  • Methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl and t-butyl are particularly preferred.
  • Alkenyl contains preferably 2 to 18, more preferably 2 to 14 and particularly preferred 2 to 12 carbon atoms.
  • the alkenyl can be linear or branched.
  • the branched alkenyl is preferably branched at the alpha or beta position with one and more, preferably two, Ci to C 6 alkyl, alkenyl or alkynyl groups.
  • Alkylene groups generally have the formula -(CH 2 )I- in which r is an integer 1 to 10. One or both of the hydrogens of at least one unit -CH 2 - can be substituted by any of the substituents mentioned below.
  • the "alkenylene” groups correspond to alkylene residues, which contain at least one double bond in the hydrocarbon backbone. If there are several double bonds, they are preferably conjugated.
  • Alkynylene groups by contrast, contain at least one triple bond in the hydrocarbon backbone corresponding to the alkylene residues.
  • the invention will be disclosed with particular reference to copper and copper nanoparticles. It should be pointed out that copper is a preferred embodiment.
  • the invention can, however, also be carried out using other conductive metals such as aluminium, zinc, nickel, cobalt and indium and similar metals which, in the present context can be characterized as being "non-noble" metals. Mixtures of two or more of copper, aluminium, zinc, nickel, cobalt and indium can also be employed.
  • the obtained particles are essentially amorphous or nanocrystalline and have a valence of copper of +1. They have, on an average, 10 to 90 %, preferably 50 - 60 % organic protectant bonded to each metal particle based on molar equivalents.
  • the organic groups surround the metal core formed by metal particles and prevent oxidation. It would appear, although this is just one possibility, that the protective groups are bonded for example to the copper particles by coordination forces or by covalent bonds.
  • the sintered metal nanoparticles depending on the metal used, generally have a resistivity of about 10 "8 to 10 "3 ohm*m, and when they are heated above about 100 0 C they will crystallize.
  • copper nanoparticles will yield crystalline copper sulphide, viz. hexagonal Cu 2 S at temperatures below 200 0 C and cubic Cui.sS at temperatures above about 200 0 C.
  • the method of producing the above described metal typically comprises the steps of reducing, in the presence of a reducing agent, dithioester monomers to the corresponding thiols while simultaneously reducing a copper precursor to the corresponding metal to yield amorphous or nanocrystalline copper nanoparticles, and recovering the nanoparticles.
  • the reactants are typically mixed together in an aqueous medium to form a reaction mixture, a reducing agent is added, and the reaction mixture is vigorously agitated to promote intimate mixing of the components during the reduction reactions.
  • the nanoparticles obtained from the reaction step are recovered by mechanical separation methods. Preferably the reaction product is recovered, and potentially filtered and washed, under inert gas protection.
  • the method is carried out by reacting, in the presence of a reducing agent, a metal precursor with an organic compound having formula II
  • R 1 has the same meaning as above, preferably it represents aryl
  • R 3 stands for an alkanoic acid which optionally bears a substituent
  • R 4 stands for an alkyl group to provide a compound having the formula I.
  • This reaction is preferably carried out in an atmosphere which contains less than 1 % oxygen.
  • the reaction is carried out in an inert atmosphere essentially free from oxygen.
  • suitable reaction gases include nitrogen, argon, helium, hydrogen and carbon dioxide and mixtures thereof. Nitrogen and argon are particularly preferred.
  • the reaction can be carried out at ambient temperature (i.e. about 20 to 25 0 C), generally the temperature is in the range of 10 to 40 0 C.
  • the reaction medium is preferably aqueous, in particular in water or in mixtures of water and other polar solvents, such as alkanols, are used.
  • R 3 stands for an alkanoic acid having 2 to 6 carbon atoms and which is substituted with at least one cyano group at an optional position.
  • Ri preferably stands for an aryl group, such as phenyl.
  • the reactant of Formula II comprises a substituted dithiobenzoate, such as 4- cyanopentanoic acid dithiobenzoate.
  • the copper precursor comprises an organic or inorganic copper (II) salt, preferably a copper (II) salt which is soluble in water.
  • the copper salt is selected from the group of copper chloride, copper nitrate, copper sulphate and copper acetate and mixtures thereof.
  • Similar inorganic or organic salts can be employed for the other metals selected from the group of Al, Zn, Ni, Co and In and mixtures thereof.
  • At least an equimolar amount of a compound according to Formula II with respect to the metal/copper precursor, preferably the compound of Formula II is used in a molar amount of 1 : 1 to 5 : 1 , in particular 1 : 1 to 3 : 1 , in respect to the copper precursor.
  • the reducing agent is a selective reducing agent.
  • the reducing agent is selected from the group of sodium borohydride, sodium cyanoborohydride, sodium dithionite, sodium triacetoxyborohydride, litium aluminium hydride, diisobutylaluminum hydride, dimethylsulphide borane, hydrazine, phenyl silane and sodium bis(2-methoxyethoxy)- aluminumhy dride .
  • the novel nanoparticles are interesting materials.
  • two samples of copper nanoparticles with different compositions were prepared using different ratios between the starting material and copper precursor (CuCl 2 ). Both samples show a feature of the amorphous state or the nanocrystalline structure from the measurements of HRTEM and selected area electron diffraction (SAED) patterns.
  • the copper nanoparticles were characterized by XPS and AES to reveal the valence of copper +1 and no oxidation.
  • it is very interesting to find that in the in situ WAXS heating experiments these copper nanoparticles crystallize upon heating up to 100 0 C and the crystalline size grows up from a few nanometer to a relatively large dimension much dependent upon temperature.
  • the crystalline structures of both samples were attributed to a hexagonal Cu 2 S at low temperatures and a cubic Cui.sS phase at high temperatures.
  • Copper sulfides (CuxS, 1 ⁇ x ⁇ 2) exist several solid phases such as Cu 2 S (chalcocite), Cu 1 ⁇ 6 S (djurleite), Cui.sS (digenite), CU1.75S (anilite), Cu 1-12 S (yarrowite), Cu 1-06 S (talnakhite) and CuS (covellite). All of these phases have been identified as p-type semiconducting materials due to copper vacancies within the lattice.
  • the present metal nanoparticles in particular copper nanoparticels, can be used for making semiconductive or conductive thin layers on a substrate.
  • substrates can be selected from group of webs and sheets of paper and cardboard and similar fibrous substrates, and various polymer materials present as films or sheets.
  • thin layers can be formed by printing or lithography and similar techniques.
  • the brown reaction mixture was first centrifuged to collect a brownish precipitate, followed by washing with deionized water and ethanol, respectively.
  • the crude product was further purified by dissolving into a tiny amount on chloroform and then precipitating with addition of hexane. All the purification was performed under N 2 protection. Finally, the product was dissolved in chloroform again, subsequently filtered using syringe filter (0.45 ⁇ m, Millipore), and dried under N 2 flow.
  • the brownish particles in the solid state kept under N 2 in freezer over six months seem stable against oxidation. Otherwise, the sample became black and was not at all soluble in chloroform.
  • the resulting copper nanoparticles were found to be hydrophobic, soluble in chloroform and THF, but not in water, ethanol, acetone, or hexane.
  • no evident absorption originates from either cyano group (CN) at ca. 2246 cm “1 or carboxylic acid (COOH) at ca. 1700 cm “1 as involved in the starting material of 4- cyanopentanoic acid dithiobenzoate (see Figure 1).
  • the spectral data suggests that the protective ligand bound to CuNPs is mainly in the form of the PhCH 2 S- that is a reduced derivative of dithiobenzoate side in the starting material of 4-cyanopentanoic acid dithiobenzoate in the above preparative reaction, where the reductant of sodium borohydride was used excessively.
  • Evidence for the above suggestion can also be found in the 1 H and 13 C NMR spectra of the as-prepared CuNPs as shown in Figure 2.
  • Figure 3 shows the percentage weight losses of both CuNPs.
  • the weight loss of the organic ligand when heating up to 800 0 C is 59.7 %, while the weight loss for CuNP -2 is 51.8 %.
  • CuNP-I contains the organic ligand ca. 8 % more than CuNP -2, most likely due to the fact that the higher molar ratio between CPAD and CuCl 2 was used in the preparation of CuNP-I, the smaller particle size was obtained. Smaller particles need more ligands to protect.
  • the as-prepared CuNPs primarily behave as amorphous nanoparticles or nanocrystallites, and their phase may inferably be sensitive to heat; to some extent, quite few nanocrystalline copper nanoparticles (less than 3 nm) may be prepared and included.
  • the as-prepared copper particles do not contain oxidized copper, that is, the copper particles are very stable against oxidation during preparation and storage.
  • XPS data in combination with Cu LMM AES spectra, makes it possible to distinguish the copper state.
  • the valence state of Cu in the as-prepared copper particles is +1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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PCT/FI2008/050543 2007-09-28 2008-09-29 Novel particles and method of producing the same WO2009040479A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20075676 2007-09-28
FI20075676A FI20075676L (fi) 2007-09-28 2007-09-28 Uudet partikkelit ja menetelmä niiden valmistamiseksi

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016045648A1 (en) 2014-09-24 2016-03-31 Univerzita Pardubice Method for preparation of a bimodal mixture of copper nanoparticles and microparticles with a polymeric protective layer, a bimodal mixture of copper nanoparticles and microparticles with a polymeric protective layer prepared by this method and a printing formula containing this bimodal mixture
EP3040140A1 (en) * 2014-12-31 2016-07-06 Institute Of Chemistry, Chinese Academy Of Sciences Method of preparing nano-copper powder and nano-copper powder prepared with the same
US10472528B2 (en) 2017-11-08 2019-11-12 Eastman Kodak Company Method of making silver-containing dispersions
US10851257B2 (en) 2017-11-08 2020-12-01 Eastman Kodak Company Silver and copper nanoparticle composites

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030199653A1 (en) * 2002-03-27 2003-10-23 Mccormick Charles L Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT
EP1500978A2 (en) * 2003-06-10 2005-01-26 Samsung Electronics Co., Ltd. Photosensitive metal nanoparticle and method of forming conductive pattern using the same
US20060254387A1 (en) * 2005-05-10 2006-11-16 Samsung Electro-Mechanics Co., Ltd. Metal nano particle and method for manufacturing them and conductive ink

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030199653A1 (en) * 2002-03-27 2003-10-23 Mccormick Charles L Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT
EP1500978A2 (en) * 2003-06-10 2005-01-26 Samsung Electronics Co., Ltd. Photosensitive metal nanoparticle and method of forming conductive pattern using the same
US20060254387A1 (en) * 2005-05-10 2006-11-16 Samsung Electro-Mechanics Co., Ltd. Metal nano particle and method for manufacturing them and conductive ink

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JUN SHUN: "Polymer Protected Gold Nanoparticles (Dissertation)", 2006, UNIVERSITY OF HELSINKI ISBN 952-10-3053-4, HELSINKI, XP002509390 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016045648A1 (en) 2014-09-24 2016-03-31 Univerzita Pardubice Method for preparation of a bimodal mixture of copper nanoparticles and microparticles with a polymeric protective layer, a bimodal mixture of copper nanoparticles and microparticles with a polymeric protective layer prepared by this method and a printing formula containing this bimodal mixture
EP3040140A1 (en) * 2014-12-31 2016-07-06 Institute Of Chemistry, Chinese Academy Of Sciences Method of preparing nano-copper powder and nano-copper powder prepared with the same
CN105798320A (zh) * 2014-12-31 2016-07-27 中国科学院化学研究所 一种低温制备纳米铜粉的方法
US10471513B2 (en) * 2014-12-31 2019-11-12 Institute Of Chemistry, Chinese Academy Of Sciences Method for preparing nano-copper powder
US10472528B2 (en) 2017-11-08 2019-11-12 Eastman Kodak Company Method of making silver-containing dispersions
US10851257B2 (en) 2017-11-08 2020-12-01 Eastman Kodak Company Silver and copper nanoparticle composites

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