US20070144305A1 - Synthesis of Metallic Nanoparticle Dispersions - Google Patents

Synthesis of Metallic Nanoparticle Dispersions Download PDF

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US20070144305A1
US20070144305A1 US11/613,136 US61313606A US2007144305A1 US 20070144305 A1 US20070144305 A1 US 20070144305A1 US 61313606 A US61313606 A US 61313606A US 2007144305 A1 US2007144305 A1 US 2007144305A1
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oxide
composition
metallic
range
nanoparticles
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Gregory Jablonski
Michael Mastropietro
Christopher Wargo
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PChem Associates Inc
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PChem Associates Inc
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Priority to US11/613,136 priority Critical patent/US20070144305A1/en
Priority to AU2006350054A priority patent/AU2006350054B2/en
Priority to EP06851795A priority patent/EP1973682A4/en
Priority to CA002634457A priority patent/CA2634457A1/en
Priority to PCT/US2006/048699 priority patent/WO2008048316A2/en
Priority to JP2008547524A priority patent/JP5394749B2/ja
Assigned to PCHEM ASSOCIATES, INC. reassignment PCHEM ASSOCIATES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JABLONSKI, GREGORY A., MASTROPIETRO, MICHAEL A., WARGO, CHRISTOPHER J.
Publication of US20070144305A1 publication Critical patent/US20070144305A1/en
Assigned to DOWA ELECTRONICS MATERIALS CO., LTD. reassignment DOWA ELECTRONICS MATERIALS CO., LTD. SECURITY AGREEMENT WITH AN EFFECTIVE DATE OF 10/10/2011 Assignors: PCHEM ASSOCIATES, INC.
Assigned to DOWA ELECTRONICS MATERIALS CO., LTD. reassignment DOWA ELECTRONICS MATERIALS CO., LTD. SECURITY AGREEMENT WITH AN EFFECTIVE DATE OF 10/10/2011 Assignors: PCHEM ASSOCIATES, INC.
Priority to JP2013140238A priority patent/JP2013254737A/ja
Assigned to PCHEM ASSOCIATES, INC. reassignment PCHEM ASSOCIATES, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: DOWA ELECTRONICS MATERIALS CO., LTD.
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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
    • 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
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of 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
    • B22F1/10—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
    • 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
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the present invention pertains to the field of nanoparticles.
  • the present invention also pertains to the fields of conductive inks and of printable conductive features.
  • Thin, conductive metal films have a wide range of uses, and have particular application as connectors in microelectronic devices, e.g., U.S. Pat. No. 6,855,378, to Subhash, N., and also as connectors in photovoltaic devices. Accordingly, the ability to make highly conductive traces and films at low temperatures and moderate cost is of enormous commercial interest to the electronics industry.
  • conductive ink systems such as those used to print membrane touch switches
  • conductive ink systems typically contain metal flake with a cross-sectional dimension of about 1000 nm as a conductive constituent and also contain polymers that function as binders.
  • These flake-based inks generally cannot be processed at temperatures lower than 120° C. or at times less than 1 minute, regardless of temperature.
  • these materials are only capable of achieving conductivities of only 2 to 10% of bulk metal conductivity because of the continuous polymeric matrix and the manner with which the flakes pack together.
  • ink systems containing flake as the metal constituent are limited in the ultimate thickness that can be obtained; because the nominal flake size is the range of 1-2 microns, the thinnest traces possible may be 3-4 microns.
  • Conductivities as high as 20% of the bulk metal are possible when using such additives, but high temperatures are needed to decompose the metallo-organic into a conductive structure, and these high temperatures accordingly limit the range substrates suitable for use in conjunction with such ink systems.
  • Some of these methods include: condensation of metal vapor to create particles, thermal decomposition of atomized metal organic salts, and use of chemically reduced metal salt solutions to produce particles. All of these production or synthesis methods require that the produced nanoparticles be stabilized in order that the nanoparticles do not interact with each other or aggregate to form larger particles that become unsuitable for a given application. Thus, preventing metallic nanoparticle aggregation can be crucial to a ink composition having maximum utility.
  • the mechanism of stabilization is important in that the manner by which agents that stabilize metallic nanoparticles against aggregation also affect the ability of the metallic particles to sinter at a low temperature.
  • a low temperature sintering process is critical to application of conductive inks to substrates, such as paper, that can not tolerate high temperatures. Affecting the ability of the metallic nanoparticles to sinter in turn defines the cure characteristics of the ink; systems that form conductive structures only after curing at temperatures above 150° C. and only after long cure times may possess such suboptimal cure behavior in part because of the method used to stabilize the particles.
  • an ideal stabilizing species prevents permanent aggregation of the particles while not interfering with the particle sintering process when heat is applied.
  • Other considerations present in choosing a stabilizing agent or agents also include the effect of the stabilizer on the nanoparticles' shelf life and their cost.
  • an aqueous metallic nanoparticle composition that exhibits little to no particle aggregation and is capable of forming a cohesive, conductive structure on a broad range of substrates after exposure to moderate temperatures for short periods of time following deposition via a printing process, and method of making such a composition.
  • a method of forming conductive structures by using such a composition is also a related need for a method of forming conductive structures by using such a composition.
  • the present invention provides, inter alia, a composition comprising a population of metallic nanoparticles dispersed in an aqueous medium, wherein at least a portion of the population comprising individual metallic nanoparticles characterized as having an average cross-sectional dimension in the range of from about 1 nm to about 100 nm.
  • the present invention provides a composition, comprising: a metallic nanoparticle mixture capable of forming a cohesive structure of less than about 10 ⁇ m in thickness following curing at a temperature of less than about 140° C. for less than about 90 seconds, wherein the cohesive structure has a resistivity in the range of from about 2 times to about 15 times the bulk resistivity of the corresponding metal.
  • the present invention provides methods for synthesizing a metallic nanoparticle dispersion.
  • the methods include reacting in an aqueous medium: at least one ligand, wherein the ligand comprises a heteroatom head group bonded to a tail comprising from 1 to about 20 carbon atoms; at least one reducing agent; and, at least one metallic salt in an aqueous dispersing solution, wherein the metallic salt is present in the dispersion at a concentration in the range of from about 10 grams/liter to about 600 grams/liter based on volume of the dispersing solution, and wherein the metallic salt comprises at least one cation comprising silver, copper, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, nickel, cobalt, indium, or any combination thereof.
  • the present invention further provides methods for forming a conductive structure on a substrate.
  • the methods comprise depositing a composition onto the substrate, wherein the composition comprises at least one population of metallic nanoparticles, wherein at least a portion of the population comprising individual metallic nanoparticles characterized as having an average cross-sectional dimension in the range of from about 1 nm to about 100 nm; wherein each of the nanoparticles comprise at least one ligand bound to its surface, the ligand comprising a heteroatom head group bound to the nanoparticle surface and a tail bound to the heteroatom head group; and, curing the deposited composition.
  • the present invention provides methods for forming a conductive structure. These methods, as will be set forth in further detail, comprise depositing a metallic nanoparticle composition onto the substrate, wherein the composition is capable of forming, after curing at a temperature of less than about 140° C. for less than about 90 seconds, a cohesive and conductive structure having a resistivity in the range of from about 2 times to about 15 times the bulk resistivity of the corresponding metal and having a thickness of less than about 20 ⁇ m, and curing the deposited composition.
  • FIG. 1 (A) depicts a transmission electron microscope (“TEM”) micrograph of silver nanoparticles synthesized by the present invention
  • FIG. 1 (B) illustrates a scanning electron microscope (“SEM”) micrograph of a trace comprised of a composition of the present invention cured for 1 minute at 100° C.;
  • FIG. 1 (C) depicts a SEM micrograph of a trace comprised of a composition of the present invention cured for 3 minutes at 85° C.;
  • FIG. 2 depicts a particle size distribution, on a weight basis, of a composition of the present invention.
  • FIG. 3 depicts the weight resistivity versus cure time for certain compositions provided by the present invention and for certain prior art compositions.
  • aqueous means containing water
  • bonding means covalently bonding, ionically bonding, hydrogen bonding, coordinate bonding, and the like.
  • tail means a straight, branched, or cyclic chain of carbon atoms, wherein the chain may be aliphatic, and wherein the chain may have one or more additional groups bound to one or more of its member carbon atoms.
  • An example would be a chain of aliphatic carbon atoms with an alcohol group attached to one of the chain members.
  • heteroatomic head group means a group including at least one atom wherein at least one atom within the group is atom other than carbon. Examples include nitrogen, sulfur, or oxygen.
  • cohesive means united as a single entity and resisting separation.
  • the term “complexing” means forming coordinating bonds with a metal atom or ion.
  • ligand means a molecule or a molecular group that binds to another chemical entity to form a larger complex. Examples include a molecular group that becomes bound to a metal or metal ion by a coordinate covalent bond through donating electrons from a lone electron pair of the ligand into an empty metal electron orbital.
  • agglomeration means two or more particles reversibly clustered together, wherein the surfaces of the particles do not come into contact with one another.
  • loc means two or more particles reversibly clustered together, wherein the surfaces of the particles do not come into contact with one another.
  • the term “bulk resistivity” means the inherent resistivity of a material that makes up a specified object.
  • the bulk resistivity of a ingot made of silver would be the inherent conductivity of silver.
  • the bulk resistivity of an ingot made of an alloy comprising silver and gold would be the inherent conductivity of the silver and gold alloy.
  • aggregate As used herein, the terms “aggregate”, “aggregation”, and similar forms mean a unified structure comprised of two or more particles irreversibly fused, connected, or necked together.
  • compositions of the present invention typically include a population of metallic nanoparticles dispersed in an aqueous medium, wherein at least a portion of the population comprising individual metallic nanoparticles characterized as having an average cross-sectional dimension in the range of from about 1 nm to about 100 nm; and, wherein each of the nanoparticles comprise at least one ligand bound to its surface, the ligand comprising a heteroatom head group bound to the nanoparticle surface and a tail bound to the heteroatom head group.
  • Nanoparticle populations typically comprise particle agglomerate comprised of two or more individual nanoparticles, nanoparticle floc comprised of two or more individual nanoparticles, or any combination thereof.
  • the ratio, by weight, of the population of individual metallic nanoparticles to particle agglomerate is contemplated as being in the range of from about 1:99 to 99:1, and the ratio, by weight, of the population of individual metallic nanoparticles to particle floc is contemplated as being in the range of from about 1:99 to 99:1.
  • a nanoparticle agglomerate has an average cross-sectional dimension in the range of from about 100 nm to about 10000 nm; a nanoparticle floc has an average cross-sectional dimension in the range of from about 100 to about 10000 nm.
  • An individual metallic nanoparticle may include silver, copper, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, nickel, cobalt, indium, silver oxide, copper oxide, gold oxide, zinc oxide, cadmium oxide, palladium oxide, iridium oxide, ruthenium oxide, osmium oxide, rhodium oxide, platinum oxide, iron oxide, nickel oxide, cobalt oxide, indium oxide, or any combination thereof.
  • the ligand tail comprises from about 1 to about 20 carbon atoms.
  • the tail can comprise a straight-chain segment, a branched segment, a cyclic segment, or any combination thereof, and can further comprise an aliphatic chain, an acid group, an alcohol group, an amphiphillic group, an amine group, and the like, or any combination thereof.
  • Suitable heteroatom head groups comprise oxygen, sulfur, nitrogen, and the like.
  • the aqueous medium comprises water, and it is envisioned that the aqueous medium can further comprise one or more polar organic solvents, one or more non-polar organic solvents, or any combination thereof.
  • a suitable polar organic solvent comprises an alcohol, a polyol, a glycol ether, 1-methylpyrolidinone, pyridine, methylethylketone, or any combination thereof.
  • a suitable non-polar organic solvent comprises tetrahydrofuran, toluene, xylene, a C 5 to C 14 branched paraffin, a C 5 to C 14 unbranched paraffin, N,N-dimethyl formamide, or any combination thereof.
  • the aqueous medium is typically capable of solvating the metallic salt in a range of from about 10 grams/liter to about 600 grams/liter, or even 50 to 200, or even 80 to 120.
  • the nanoparticles are present in the range of from about 0.5 wt % to about 70 wt %, the ligand is present in the range of from about 0.5 wt % to about 75 wt %, and the medium is present in the range of from about 30 to about 98 wt %.
  • the composition is capable of forming a cohesive structure of less than about 10 ⁇ m in thickness following curing at a temperature of less than about 110° C. for less than about 90 seconds.
  • the structure suitably has a resistivity in the range of from about 2 times to about 15 times the bulk resistivity of the corresponding metals present in the composition.
  • Compositions also comprise a metallic nanoparticle mixture capable of forming a cohesive structure of less than about 10 ⁇ m in thickness following curing at a temperature of less than about 110° C. for less than about 60 seconds, or capable of forming a cohesive structure of less than about 5 ⁇ m in thickness following curing at a temperature of less than about 140° C. for less than about 15 seconds, or capable of forming a cohesive structure of less than about 2 ⁇ m in thickness following curing at a temperature of less than about 110° C. for less than about 10 seconds, or capable of forming a cohesive structure of less than about 2 ⁇ m in thickness following curing at a temperature of less than about 140° C. for less than about 5 seconds, wherein the cohesive structure has a resistivity in the range of from about 2 times to about 15 times the bulk resistivity of the corresponding metal in the composition.
  • Suitable mixtures comprise a population of metallic nanoparticles, a ligand, an aqueous medium, or any combination thereof.
  • the metallic nanoparticle populations can comprise individual nanoparticles, particle agglomerate comprised of two or more individual nanoparticles, particle floc comprised of two or more individual nanoparticles, or any combination thereof.
  • the ratio, by weight, of the population of individual metallic nanoparticles to particle agglomerate can be in the range of from about 1:99 to 99:1, and the ratio, by weight, of the population of individual metallic nanoparticles to particle floc is typically in the range of from about 1:99 to 99:1.
  • substantially all of the nanoparticles are agglomerated.
  • substantially all of the nanoparticles are discrete individual nanoparticles.
  • individual metallic nanoparticles have an average cross-sectional dimension in the range of from about 1 nm to about 100 nm; or even from about 5 nm to about 30 nm, or even from about 10 nm to about 20 nm.
  • Particle size can be measured using an acoustic attenuation spectroscopy method substantiated by transmission electron microscopy.
  • Particle agglomerates have an average cross-sectional dimension of at least about 2 nm, or even at least about 20 nm, or even at least about 200 nm, or in the range of from about 100 nm to about 10000 nm; and particle flocs have an average cross-sectional dimension in the range of from about 100 to about 10000 nm.
  • Individual metallic nanoparticles and ligands are as described elsewhere herein; ligands are typically characterized as bound to a surface of one or more metallic nanoparticles by a heteroatom head group so as to give rise to one or more metallic nanoparticles stabilized against irreversible aggregation.
  • the aqueous medium of these compositions typically comprises water, and can further comprise one or more polar organic solvents, one or more non-polar organic solvents, or any combination thereof.
  • the aqueous medium is typically capable of solvating the metallic salt in a range of from about 10 grams/liter to about 600 grams/liter, and suitable polar organic solvents include an alcohol, a polyol, a glycol ether, 1-methylpyrolidinone, pyridine, methylethylketone, or any combination thereof.
  • Suitable non-polar organic solvents comprises tetrahydrofuran, toluene, xylene, a C 5 to C 14 branched paraffin, a C 5 to C 14 unbranched paraffin, N,N-dimethyl formamide, or any combination thereof.
  • the nanoparticles can be present in the range of from about 0.5 to about 70 wt %, the ligand can be present in the range of from about 0.5 to about 75 wt %, and the medium can be present in the range of from about 30 to about 98 wt %.
  • the nanoparticles can be present in the range of from about 10 to about 60 wt %, the ligand can be present in the range of from about 1 to about 30 wt %, and the medium is present in the range of from about 30 to about 98 wt %.
  • the nanoparticles can be present in the range of from about 15 to about 55 wt %, the ligand is present in the range of from about 2 to about 25 wt %, and the medium is present in the range of from about 30 to about 98 wt %. Also, the amount of ligand can be about 10% based on weight relative to the weight of the nanoparticles.
  • the present invention involves the chemical reduction of metal salt in the presence of a ligand, which ligand is capable of complexing or bonding to the metal in a dispersing medium.
  • the metal salt can be solvated by the solvent or dispersed in the solvent as a solid if the salt is insoluble in the solvent phase.
  • Suitable solvents include aqueous solvents substantially free of organic solvents.
  • Suitable solvents also include some polar organic solvents, e.g., if the metal salt can be solvated in a sufficiently high concentration, e.g., about 0.3 to about 0.9 M, or about 0.45 to about 0.7 M, or about 0.55 to about 0.6 M.
  • the metal may include silver, copper, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, nickel, cobalt, indium, or any combination thereof.
  • the salt anion may include nitrates, carboxylates, sulfates, or chlorides.
  • the reducing agent must be of sufficient electrochemical potential and concentration to effectively reduce the respective metal salt. Strong reducing agents such as hydrazine, hydrazine hydrate, or hydrogen, that do not produce undesirable ionic byproducts are suitable; other reducing agents such as sodium borohydride may be used.
  • Ligands can be chosen on their ability to complex with metal particles and stabilize the particles against aggregation; one consideration is the ability of the ligand to allow the particles to consolidate and sinter during drying and thermal treatment. The temperature at which the particles sinter is in some part controlled by the ligand adsorbed to the metal.
  • the ligand can be characterized as bonding to the metal through a heteroatom such as oxygen, sulfur, or nitrogen. In some embodiments the heteroatom portion of the ligand is provided as a carboxyl, sulfonyl, thiol, and the like.
  • an intermediate salt may result during thermal treatment that adversely affecting the sintering of the metal nanoparticles.
  • Ligands having a straight-chain aliphatic backbone comprising from about 1 to about 20 carbon atoms are particularly suitable. Branched or cyclic backbones having up to about 20 carbon atoms may be used, for example, if the ligand is sufficiently stable in the solvent system. Suitable ligands can preferably have from about 5 to about 12 carbon atoms in the aliphatic tail.
  • no post-synthesis treatment such as washing or phase transfer is needed in order to remove residual byproducts such as the metal salt anion.
  • this step is not needed, additional washing and post-processing steps can be used.
  • the byproducts of the reaction are left in the nanoparticle mixtures to catalyze the decomposition of the ligands on the nanoparticles surface.
  • nitrate anions can react with organic acid ligands in self-propagating chemical decomposition or anionic oxidation-reduction synthesis of superconducting oxides to prevent intermediate metal salts.
  • a compound such as an amine could be added to the reaction product or be part of the ligand molecule which similarly catalyzes the decomposition of the ligands and sintering of the nanoparticles.
  • the particles are sometimes allowed to settle in order to concentrate them for forming films.
  • the metallic nanoparticles are able to remain dispersed in the aqueous phase by the formation of self-assembled surfactant structures, e.g., an interdigitated bi-layer, of the ligand or vesicle structures around the metallic nanoparticles.
  • the nanoparticles can phase separate from the aqueous phase giving rise to an oily ligand-rich phase comprising concentrated nanoparticles and a second aqueous phase.
  • the particles can be stabilized by ligands binding to the surface of the silver through nucleophilic head groups with the aliphatic portion extending outward.
  • the aliphatic portion of ligands not bound to the nanoparticle surface can associate with the aliphatic portion of the bound ligands forming a vesicle around the nanoparticle.
  • the metallic nanoparticles may phase-separate into an oily phase.
  • ligands can form a bi-layer around the particles. The bi-layer can be broken down causing the nanoparticles to form a hydrophobic phase by either modifying the pH or by adding a salt or to the aqueous sol.
  • methods for synthesizing a metallic nanoparticle dispersion include reacting in an aqueous medium: at least one ligand, wherein the ligand comprises a heteroatom head group bonded to a tail comprising from 1 to about 20 carbon atoms; at least one reducing agent; and, at least one metallic salt in an aqueous dispersing solution, wherein the metallic salt is present in the dispersion at a concentration in the range of from about 10 grams/liter to about 600 grams/liter based on volume of the dispersing solution, and wherein the metallic salt comprises at least one cation comprising copper, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, nickel, cobalt, indium, or any combination thereof.
  • the metallic salt comprises silver.
  • the tail is as described elsewhere herein;
  • suitable heteroatom head groups comprise oxygen, sulfur, nitrogen, and the like.
  • a suitable ligand is characterized as being capable of binding by its heteroatom head group to a surface of a metallic nanoparticle so as to give rise to a metallic nanoparticle stabilized at least in part against aggregation.
  • Suitable reducing agents include strong reducing reagents that typically are capable of reducing metals in aqueous systems, e.g., hydrazine, hydrazine hydrate, hydrogen, sodium borohydride, lithium borohydride, ascorbic acid, a primary amine, a secondary amine, a secondary amine, a tertiary amine, and the like, or any combination thereof.
  • strong reducing reagents that typically are capable of reducing metals in aqueous systems, e.g., hydrazine, hydrazine hydrate, hydrogen, sodium borohydride, lithium borohydride, ascorbic acid, a primary amine, a secondary amine, a secondary amine, a tertiary amine, and the like, or any combination thereof.
  • the metallic salt typically comprises at least one anion, wherein the anion comprises acetate, nitrate, carboxylate, sulfate, chloride, hydroxide, or any combination thereof.
  • a suitable dispersing solution comprises an aqueous medium.
  • Another suitable dispersing solution comprises an aqueous medium substantially free of organic solvents, and can comprise water.
  • the dispersing solution can further comprise one or more polar organic solvents, one or more non-polar organic solvents, or any combination thereof. Suitable polar and non-polar solvents are as described elsewhere herein.
  • Reacting can comprise contacting, mixing, stirring, sonicating, agitating, and the like; after reacting, one or more ligand heteroatom head groups are characterized as bound to a surface of one or more metallic nanoparticles so as to give rise to one or more metallic nanoparticles stabilized against irreversible aggregation.
  • the method typically comprises combining the ligand and metallic salt in a respective molar ratio in the range of from about 0.1:1 to about 0.2:0.7, or even in the range of from about 0.1:1 to about 0.3:0.5; combining the metallic salt and reducing agent in a respective molar ratio in the range of from about 0.7:1 to about 1:2, in other cases the metallic salt and reducing agent in a respective molar ratio in the range of from about 4:1 to about 1:2, in other cases the metallic salt and reducing agent in a respective molar ratio in the range of from about 0.6:1 to about 1.2:1.
  • the method can, in some embodiments, include adjusting the relative amounts of ligand, reducing agent, metallic salt, aqueous dispersing solution, adjusting the pH of the aqueous medium, or any combination thereof, so as to give rise to a pH in the range of from about 3 to about 12.
  • the pH can vary between the basic and acidic regimes during the reaction.
  • the method includes heating the aqueous medium, ligand, reducing agent, and metallic salt in aqueous dispersing solution, or any combination thereof, to a temperature of from about 5° C. to about 200° C. prior to reaction, to a temperature of from about 35° C. to about 70° C. prior to reaction, or to a temperature of from about 40° C. to about 60° C. prior to reaction.
  • the method typically includes a recovery step following reaction.
  • the recovery step can include allowing the passage of sufficient time such that the concentration of nanoparticles in any aqueous medium present after reaction can be in the range of from about 0 wt % to about 70 wt %, or in the range of from about 0.5 wt % to about 30 wt. %, or in the range of from about 2 wt % to about 20 wt. %, or in the range of from about 3 wt % to about 7 wt. %, and then recovering the reaction products.
  • the recovery step comprises allowing the passage of sufficient time such that the concentration of nanoparticles in any aqueous medium present can be in the range of from about 0.5 wt % to about 70 wt. %, or in the range of from about 5 wt % to about 60 wt. %, decanting the aqueous medium, recovering the reaction products, and ultrafiltration of the decanted aqueous medium to recover any nanoparticles residing in the decanted medium.
  • a cake comprising nanoparticles will be formed. Such a cake can have from about 25 wt. % to about 70 wt. %.
  • a supernatant is formed, which can comprise from 0 wt.
  • the recovery step can include ultrafiltration of any aqueous medium present following reaction when there are no settled reaction products so as to recover nanoparticles present in the medium.
  • the reacting comprises continuously introducing the aqueous medium, ligand, and reducing agent into a first stirred reactor capable of fluid communication with the contents of a second stirred reactor.
  • Suitable medium, ligand, and reducing agent are described elsewhere herein, as are the suitable ratios of these entities to one another.
  • the aqueous medium, ligand, reducing agent, and metallic salt in aqueous dispersing solution may be heated as set forth elsewhere herein.
  • the residence time of the first reactor is sufficient to as to give rise to the reaction progressing to substantial completion, and the method can include continuously transporting the contents of the first reactor to the second reactor; the residence time in the second reactor is envisioned as sufficient to allow the reaction to progress to essentially total completion.
  • the methods described herein can also include one or more recovery steps.
  • FIGS. 1 (A), 1 (B), and 1 (C) depict metallic nanoparticles synthesized according to the present invention and the structures formed by curing these nanoparticles.
  • FIG. 1 (A) depicts silver nanoparticles made according to the present invention. As can be seen by comparison of the particles to the scale bar in FIG. 1 (A), typical nanoparticles made in accordance with the present invention have widths of well under 100 nm.
  • FIG. 1 (B) depicts a structure formed by metallic nanoparticles made according to the present invention after curing at about 100° C. for about 1 minute.
  • FIG. 1 (C) depicts a structure formed by metallic nanoparticles made according to the present invention after curing at about 85° C. for about 3 minutes.
  • FIG. 2 The existence of individual particles along with nanoparticle agglomerate in certain embodiments of the present invention is shown in FIG. 2 . That figure depicts, on a weight basis, the proportion of individual metallic nanoparticles synthesized according to the present invention relative to nanoparticle agglomerate comprised of the individual nanoparticles.
  • Methods for forming a conductive structure on a substrate comprise depositing a composition onto the substrate, wherein the composition comprises at least one population of metallic nanoparticles, at least a portion of the population comprising individual metallic nanoparticles characterized as having an average cross-sectional dimension in the range of from about 1 nm to about 30 nm; wherein each of the nanoparticles comprise at least one ligand bound to its surface, the ligand comprising a heteroatom head group bound to the nanoparticle surface and a tail bound to the heteroatom head group; and, curing the deposited composition.
  • the depositing can include a printing method; suitable printing methods include flexographic printing, rotogravure printing, lithographic printing, intaglio printing, relief printing, screen printing, inkjet printing, laser printing, or any combination thereof.
  • typical populations of metallic nanoparticles are as described elsewhere herein, as are suitable ligands, and acceptable aqueous media.
  • the ink rheology is influenced by the deformation behavior of the solid components and the flow behavior of the components. Mezger, T. G., The Rheology Handbook, 2002, published by Vincentz Verlag, Hannover, Germany; Verstrat, D. W., Research Report, Formulating with Associative Rheology Modifiers, Alco Chemical website, www.alcochemical.com., Alco Chemical Company, Division of National Starch and Chemical Company, Chattanooga, T N; Manshausen, P., Borchers GmbH, Monheim, Germany, Presented at the 6 th Nurnberg Congress, April, 2001.
  • Additives can modify the ink rheology such that the desired flow properties are achieved with minimal adverse affects on the electrical properties and adhesion of the metallic trace or film.
  • Associative thickeners generally associate with ingredients in the inks such as the metal nanoparticles and the polymeric binder particles incorporated for adhesion.
  • Non-associative thickeners interact with the aqueous phase, essentially thickening the water.
  • the composition of the method can include one or more rheology modifiers.
  • Some such modifiers can include an associative thickener such as hydrophobically modified polyether polyurethane, hydrophobically modified polyether, hydrophobically modified acrylic thickener, hydrophobically modified cellulose ether, and the like.
  • the rheology modifier can include a thickening agent such as an alkali-soluble emulsion, such as a polymer comprising units polymerized from (meth)acrylic acid, wherein a suitable polymer comprises a homopolymer of (meth)acrylic acid, a co-polymer of (meth)acrylic acid and (meth)acrylate esters, maleic acid, or any combination thereof.
  • a thickening agent can also include a cellulose based material such as hydroxyethyl cellulose, hydroxypropyl cellulose, arabinogalactin, dextran, starches, an acid swellable emulsion, a polyvinyl alcohol, a polyacrylamide, polyethylene glycol, or any combination thereof.
  • a rheology modifier can be present in the range of from about 0 wt % to about 15 wt %, or in the range of from about 0 wt % to about 7 wt %, or even in the range of from about 0 wt % to about 3 wt %.
  • Preparation of a formulation that is viable as an ink to be printed on commercial printing equipment also typically requires the addition of agents to enable or enhance adhesion of the cured ink to the desired substrate, to enhance the wetting of the ink on the substrate, and to modify the rheological or flow characteristics of the ink.
  • metallic nanoparticles will not adhere to untreated substrates that are commonly used such as polyester, polypropylene, and paper.
  • adhesives, binders, or any combination thereof may be added to the metallic nanoparticle dispersion such that additive establishes a chemical or physical bond with the surface of the desired substrate.
  • these additives do not prevent or hamper the process of curing or sintering the metallic nanoparticles into a continuous, conductive film or structure.
  • the adhesion-enhancing additive should be chosen such that it does not affect the stability of the nanoparticles.
  • Adhesion-promoting additives generally include surfactants that contribute to the ink wetting the substrate surface.
  • the composition of the disclosed method further comprises a binder, which can include a latex, any polymer soluble in the solvent medium of the nanoparticles, or compatible with the nanoparticles, a polymer latex, an emulsion polymer, polyimide, a silicone, a fluorocarbon, a polyamic acid, a polyurethane, a polyester, an epoxy, polyvinylalcohol, polyacrylamide, or any combination thereof.
  • a binder which can include a latex, any polymer soluble in the solvent medium of the nanoparticles, or compatible with the nanoparticles, a polymer latex, an emulsion polymer, polyimide, a silicone, a fluorocarbon, a polyamic acid, a polyurethane, a polyester, an epoxy, polyvinylalcohol, polyacrylamide, or any combination thereof.
  • the binder is present in the range of from about 0 wt % to about 20 wt %, or in the range of from about 0 wt % to about 7 wt %., or in the range of from about 0 wt % to about 5 wt %.
  • Substrates suitable for the method include a glass, a ceramic, a polymer, a silicon, a nitride, a carbides, a ceramic precursor, or any combination thereof.
  • Suitable polymers include a polyester, a polyolefin, a polycarbonate, an acrylic polymer, polyethylene naphthalate, polyimide, polyamideimide, polyvinyl chloride, polypropylene, a liquid crystal polymer, polycarbonate, or any combination thereof.
  • the substrate comprises paper, synthetic engineered paper, cardboard, a coated corrugated cardboard, uncoated corrugated cardboard, a fabric, and the like.
  • At least a portion of a surface of the substrate is capable of being modified to give rise to a surface capable of adhering to the deposited composition.
  • the composition further comprises metallic particles.
  • Such particles typically have a width in the range of from about 200 nm to about 20000 nm, in the range of from about 500 nm to about 10000 nm, or in the range of from about 800 nm to about 3000 nm.
  • Suitable particles comprise silver, copper, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, nickel, cobalt, indium, silver oxide, copper oxide, gold oxide, zinc oxide, cadmium oxide, palladium oxide, iridium oxide, ruthenium oxide, osmium oxide, rhodium oxide, platinum oxide, iron oxide, nickel oxide, cobalt oxide, indium oxide, or any combination thereof.
  • the curing aspect of the method typically comprises exposing the deposited composition to a temperature of less than about 110° C. for less than about 90 seconds; a structure formed by the method typically has a thickness of less than about 20 ⁇ m; or exposing the deposited composition to a temperature of less than about 110° C. for less than about 60 seconds; a structure formed by the method typically has a thickness of less than about 15 ⁇ m; or exposing the deposited composition to a temperature of less than about 140° C. for less than about 30 seconds; a structure formed by the method typically has a thickness of less than about 15 ⁇ m; or exposing the deposited composition to a temperature of less than about 110° C.
  • a structure formed by the method typically has a thickness of less than about 8 ⁇ m; or exposing the deposited composition to a temperature of less than about 140° C. for less than about 20 seconds; a structure formed by the method typically has a thickness of less than about 8 ⁇ m.
  • Methods for forming a conductive structure include depositing a metallic nanoparticle composition onto the substrate, wherein the composition is capable of forming after curing at a temperature of less than about 110° C. for less than about 90 seconds a cohesive and conductive structure having a resistivity in the range of from about 2 times to about 15 times the bulk resistivity of the corresponding metal and having a thickness of less than about 20 ⁇ m; and, curing the deposited composition.
  • Nanoparticle compositions are envisioned as including a population of metallic nanoparticles, a ligand, a medium, or any combination thereof, all as discussed elsewhere herein.
  • compositions further can also include rheology modifiers as described elsewhere herein.
  • the composition is envisioned as further comprising a binder, as described elsewhere herein.
  • Suitable compositions may also include metallic particles, as detailed elsewhere.
  • FIG. 3 depicts resistivity as a function of cure time for prior art compositions and compositions provided by the present invention.
  • the resistivity of a composition comprising metallic silver nanoparticles synthesized by the present invention achieve a resistivity comparable to that of bulk silver (trace (a)) after curing at a temperature of about 85° C. for about 1 minute.
  • Trace (c) represents a composition comprising metallic silver nanoparticles synthesized by the present invention and certain additives such as rheology modifiers and binders; as shown, that composition also approaches the resistivity of bulk silver after curing at a temperature of about 100° C. for about 6 minutes.
  • Trace (d) represents a composition produced by Sumitomo Metal Mining Co (Japan), http:www.smm.co.jp/b_info_E/b10_E.html which composition, when cured at 150° C., achieved resistivity higher than that of compositions made according to the present invention at all cure times.
  • Trace (e) represents a composition produced by Sumitomo (Japan), which, when cured at 100° C., and also is characterized as having a resistivity several orders of magnitude greater than that of compositions made according to the present invention at all cure times.
  • An initial solution was prepared by adding 7.5 grams of ammonium hydroxide (30% ammonia by weight) to 275 grams of water; 13.5 grams of heptanoic acid was added to this solution followed by 20.9 grams of 50% hydrazine hydrate aqueous solution.
  • the ammonium hydroxide is necessary to allow the acid to dissolve in the water.
  • 36 grams of silver nitrate was dissolved in 175 grams of water.
  • the silver nitrate solution was added to the initial solution while stirring under nitrogen.
  • the resultant product was flocculated and allowed to settle. Excess water was decanted off.
  • the concentrated product was spread onto 5 mil polyester film with a 0.5 mil wire wound rod and then cured at 80° C. and 100° C. for 1-2 minutes resulting in cohesive and conductive silver films.
  • An initial solution was prepared by adding 2.1 grams of ammonium hydroxide (30% ammonia by weight) to 50 grams of water; 7.8 grams of heptanoic acid was added to this solution followed by 3 grams of 50% hydrazine hydrate aqueous solution. Separately, 10 grams of silver nitrate was dissolved in 50 grams of water. The silver nitrate solution was added to the initial solution while stirring under nitrogen. The resultant product was allowed to settle and the excess water decanted off.
  • the concentrated product was spread onto 5 mil polyester film with a 0.5 mil wire wound rod and then cured at 80° C. and 100° C. for 1-2 minutes resulting in cohesive and conductive silver films.
  • the weight resistivity of a sample cured at 100° C. for 1 minute was measured to be 0.39 gram-ohms/m 2 ( ⁇ 2 ⁇ bulk silver).
  • An ink composition was prepared by adding 50 grams of spherical silver powder (1-2 um mean diameter) to 50 grams of 35 wt % nanoparticle dispersion of Example 1 also containing 3 wt % of an acrylic copolymer latex (55 wt % polymer), 2 wt % of polyvinyl alcohol (25 wt % in water, M w of 8,000-9,000), and 1 wt % ethylene glycol. The materials were mixed well together, and were milled in a mortar and pestle until a homogeneous mixture was obtained. A film of the resulting ink was deposited onto 0.005′′ thick untreated polyester film with a 0.0015′′ Bird film applicator. The wet film was cured in a 100° C.
  • the weight resistivity of the resulting silver films was measured to be 1.3 gram-ohms/m 2 , approximately 8 times the resistivity of bulk silver.
  • the adhesion of the film to the substrate was tested by applying a 4′′ long strip of Scotch brand tape (3M Corporation) to the film, insuring good adhesion to the film by applying pressure with the index finger (not the fingernail). The tape is then rapidly removed, pulling upward at a 90° angle, perpendicular to the substrate.
  • This tape test method is derived from the ASTM D3359-02 Standard Test Method for Measuring Adhesion by Tape Test. Slight removal of the silver from the bulk of the trace was observed (4.215, with 5 being a clean tape), but none of the silver was removed from the substrate. The failure was observed to be a cohesive failure between the silver particles.
  • An ink composition was prepared by adding 50 grams of spherical silver powder (1-2 micron mean diameter) to 50 grams of 35 wt % nanoparticle dispersion also containing 10 wt % polyvinlacetate-polyethylene copolymer latex (50 wt % polymer), 2 wt % of polyvinyl alcohol (25 wt % in water, Mw of 8,000-9,000), and 1 wt % ethylene glycol. The materials were mixed well together, and were milled in a mortar and pestle until a homogeneous mixture was obtained. A film of the resulting ink was deposited onto 0.005′′ thick untreated polyester film with a #16 wire wound rod (0.016′′ wire diameter, 0.001′′ wet film thickness).
  • the wet film was cured in a 100° C. for 30 seconds followed by 30 seconds at 140° C.
  • the weight resistivity of the resulting silver films was measured to be 1.0 gram-ohm/m 2 , approximately 6.2 times the resistivity of bulk silver.
  • the adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described in Example 2. The adhesion of the film to the substrate was very good (4.8/5), with only a trace of silver removed from the surface (cohesive failure), and no silver removal from the substrate was observed.
  • An ink composition was prepared by adding 25 grams of spherical silver powder (1-2 um mean diameter) to 50 grams of 35 wt % nanoparticle dispersion also containing 3 wt % acrylic copolymer (55 wt % polymer), and 4 wt % of polyacrylamide (50 wt % in water). The materials were mixed well together, and were milled in a mortar and pestle until a homogeneous mixture was obtained. A film of the resulting ink was deposited onto 0.005′′ thick untreated polyester film with a #16 wire wound rod (0.016′′ wire diameter, 0.001′′ wet film thickness). The wet film was cured in a 100° C. for 30 seconds followed by 60 seconds at 130° C.
  • the weight resistivity of the resulting silver films was measured to be 1.71 gram-ohms/M 2 , approximately 10.7 times the resistivity of bulk silver.
  • the adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described in Example 2. The adhesion of the film to the substrate was very good (4.8/5), with only a trace of silver removed from the surface (cohesive failure), and no silver removal from the substrate was observed.
  • An ink composition was prepared by adding 65 grams of spherical silver powder (1-2 pm mean diameter) to 80 grams of 35 wt % nanoparticle dispersion also containing 3 wt % acrylic copolymer (55 wt % polymer), 1.5 wt % of polyacrylamide (50 wt % in water), and 1 wt % propylene glycol. The materials were mixed well together, and were milled in a mortar and pestle until a homogeneous mixture was obtained. A film of the resulting ink was deposited onto 0.005′′ thick untreated polyester film with a #16 wire wound rod (0.016′′ wire diameter, 0.001′′ wet film thickness). The wet film was cured in a 100° C.
  • the weight resistivity of the resulting silver films was measured to be 1.31 gram-ohms/m 2 , approximately 8 times the resistivity of bulk silver.
  • the adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described in Example 2. The adhesion of the film to the substrate was good (4.215), with some removal (cohesive failure) of the silver from the bulk of the trace (4.215, with 5 being a clean tape), but no silver removal from the substrate.
  • An ink composition was prepared by adding 52 grams of spherical silver powder (1-2 ⁇ m mean diameter) to 64 grams of 35 wt % nanoparticle dispersion also containing 3 wt % acrylic copolymer (55 wt % polymer), 1.5 wt % of polyacrylamide (50 wt % in water), and 1 wt % propylene glycol. The materials were mixed well together, and were further mixed in vortex paint mixer for 5 minutes. A film of the resulting ink was deposited onto 0.005′′ thick untreated polyester film with a #16 wire wound rod (0.016′′ wire diameter, 0.001′′ wet film thickness). The wet film was cured in a 60° C. for 20 seconds followed by 40 seconds at 130° C.
  • the weight resistivity of the resulting silver films was measured to be 1.00 gram-ohms/m 2 , approximately 6 times the resistivity of bulk silver.
  • the adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described in Example 2. The adhesion of the film to the substrate was very good (4.9/5), with only a slight trace of silver removed from the surface (cohesive failure), and no silver removal from the substrate was observed. Further, resulting samples were folded in expansive mode (single crease) and than compressive mode (single crease), and a hard crease was made with the tip of the finger (not the finger nail) on each sample. Minimal loss of conductivity was observed for each sample.
  • An ink composition was prepared by adding 10 grams of Floetrol (The Flood Company) to 40 grams of 35 wt % nanoparticle dispersion. The materials were mixed well together and a film of the resulting ink was deposited onto 0.005′′ thick untreated polyester film with a 0.0005′′ diameter wire wound rod and then cured at 130° C. for 90 seconds resulting in cohesive and conductive silver films.
  • the adhesion of the film to the substrate was tested by applying a 4′′ long strip of Scotch brand tape (3M Corporation) to the film, insuring good adhesion to the film by applying pressure with the index finger (not the fingernail). The tape is then rapidly removed, pulling upward at a 90′ angle, perpendicular to the substrate.
  • This tape test method is derived from the ASTM D3359-02, Standard Test Method for Measuring Adhesion by Tape Test. No material was removed from the substrate.
  • An ink composition was prepared by adding 10 grams of a 25 wt % solution of polyvinyl alcohol (9,000-10,000 Mw, 80% hydrolyzed) to 40 grams of 35 wt % silver nanoparticle dispersion. The materials were mixed well together and a film of the resulting ink was deposited onto 0.005′′ thick polyester film with a 0.0005′′ diameter wire wound rod and then cured at 130° C. for 90 seconds resulting in cohesive and conductive silver films. The adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described. Some material was removed from the substrate, however, most of the ink remained on the substrate.
  • a film of the as-prepared, 35 wt % silver nanoparticle dispersion was deposited onto 5 mil polyester film with a 0.0005′′ diameter wire wound rod and then cured at 85° C. for 60 seconds resulting in cohesive and conductive silver films.
  • the resulting film had a weight resistivity of 0.38 gram-ohms/m2 (IPC-TM-650, number 2.5.17.2).
  • the adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described. All of the material was removed from the substrate.
  • An ink composition was prepared by adding 2.6 grams of a 1 or 2 wt % solution of commercially available hydrophobically modified hydroxyethylcellulose to 19.2 grams of 40 wt % silver nanoparticle dispersion. The materials were mixed well together and a film of the resulting ink was deposited onto 0.005′′ thick polyester film with a 0.0003′′ diameter wire wound rod and then cured at 130° C. for 90 seconds resulting in a cohesive and conductive silver film. The adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described. All of the material was removed from the substrate.
  • An ink composition was prepared by adding 0.5 grams of a solution of hydrophobically modified ethoxylated urethane rheology modifier to 10 grams of 34 wt % silver nanoparticle dispersion. The materials were mixed well together and a film of the resulting ink was deposited onto 0.005′′ thick polyester film with a 0.0003′′ diameter wire wound rod and then cured at 100° C. for 60 seconds resulting in a cohesive and conductive silver film. The adhesion of the film to the substrate was tested using the tape test method described above. All of the material was removed from the substrate.
  • An ink composition was prepared by adding 0.36 grams of Arabinogalactan wood gum (Larex Grade 100) to 18.2 grams of 35 wt % silver nanoparticle dispersion. The materials were mixed well together and a film of the resulting ink was deposited onto 0.005′′ thick polyester film with a 0.0003′′ diameter wire wound rod and then cured at 100° C. for 60 seconds resulting in a cohesive and conductive silver film. The adhesion of the film to the substrate was tested using the tape test method described above. Some of the material was removed.
  • An ink composition was prepared by adding 0.63 grams of a 50 wt. % polyacrylamide solution (Aldrich 10,000 Mw) to 12.57 grams of 40 wt % silver nanoparticle dispersion. The materials were mixed well together and a film of the resulting ink was deposited onto 0.005′′ thick polyester film with a 0.0003′′ diameter wire wound rod and then cured at 100° C. for 60 seconds resulting in a cohesive and conductive silver film. The adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described in Example 1. None of the material was removed from the substrate.
  • An ink composition was prepared by adding 0.44 grams of a 25 wt. % polyvinyl alcohol solution (Aldrich 9,000-10,000 Mw) and 1.14 grams of an acrylic nanoparticle latex dispersion to 22.2 grams of 35 wt % silver nanoparticle dispersion. The materials were mixed well together and a film of the resulting ink was deposited onto 0.005′′ thick polyester film with a 0.0003′′ diameter wire wound rod and then cured at 130° C. for 30 seconds resulting in a cohesive and conductive silver film. The adhesion of the film to the substrate was evaluated by utilizing the tape test method previously described in Example 2. Some of the material was removed from the substrate was removed from the substrate
  • Example 1 The material of Example 1 was transferred to hexane by sodium chloride induction similar to the method of Hirai. Hirai, et al., Chemistry Letters, 1992, 1527-1530; Hirai, et al., J. of Colloid and Interface Sci., 1993, 161, 471-474. Hexane and a sodium chloride solution was added to concentrated material from Example 1 and the two phases mixed with a magnetic stir bar for 10 minutes. The silver nanoparticles transferred phases to the non-aqueous phase presumably leaving all ionic species in the aqueous phase. The solvent phase with the suspended silver particles was separated from the water phase. When an attempt was made to cure the phase transferred material at 120° C., the silver did not cure and an oily silver film remained even after extended periods at this temperature.
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