WO2012161857A1 - Procédés de préparation de nanofils, compositions et articles - Google Patents

Procédés de préparation de nanofils, compositions et articles Download PDF

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WO2012161857A1
WO2012161857A1 PCT/US2012/029322 US2012029322W WO2012161857A1 WO 2012161857 A1 WO2012161857 A1 WO 2012161857A1 US 2012029322 W US2012029322 W US 2012029322W WO 2012161857 A1 WO2012161857 A1 WO 2012161857A1
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Prior art keywords
atom
metal
ion
compound
halide
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PCT/US2012/029322
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English (en)
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David R. Whitcomb
William D. Ramsden
Doreen C. Lynch
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Carestream Health, Inc.
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Priority claimed from US13/326,356 external-priority patent/US8613887B2/en
Priority claimed from US13/420,635 external-priority patent/US20120183435A1/en
Application filed by Carestream Health, Inc. filed Critical Carestream Health, Inc.
Publication of WO2012161857A1 publication Critical patent/WO2012161857A1/fr

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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
    • B22F1/0547—Nanofibres or nanotubes
    • 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
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution

Definitions

  • the general preparation of silver nanowires (10-200 aspect ratio) is known. See, for example, Angew. Chem. Int. Ed. 2009, 48, 60, Y. Xia, Y. Xiong, B. Lim, S. E. Skrabalak, which is hereby incorporated by reference in its entirety. Such preparations typically employ Fe 2+ or Cu 2+ ions to "catalyze" the wire formation over other morphologies.
  • the controlled preparation of silver nanowires having desired lengths and widths is not known. For example, the Fe 2+ produces a wide variety of lengths or thicknesses and the Cu 2+ produces wires that are too thick for many applications.
  • metal halide salts FeCl 2 or CuCl 2 When iron or copper are used, they are typically provided as the metal halide salts FeCl 2 or CuCl 2 . See, for example, B. Wiley et al., Nano Letters, 2004, 4, 1733-1739 and K.E. Korte et al., J. Mats. Chem., 2008, 18, 437.
  • Other metal halide salts have been used in nanowire synthesis. See, for example, J. Jiu, K. Murai, D. Kim, K. Kim, K. Suganuma, Mat. Chem. & Phys., 2009, 114, 333, which refers to NaCl, CoCl 2 , CuCl 2 , NiCl 2 and ZnCl 2 , and S.
  • Nandikonda "Microwave Assisted Synthesis of Silver Nanorods," M.S. Thesis, Auburn University, Auburn, Alabama, USA, August 9, 2010, which refers to NaCl, KC1, MgCl 2 , CaCl 2 , MnCl 2 , CuCl 2 , and FeCl 3 .
  • Use of KBr has been disclosed in, for example, D. Chen et al., /. Mater. Set: Mater. Electron., 2011, 22(1), 6-13; L. Hu et al., ACS Nano, 2010, 4(5), 2955-2963; and C. Chen et al, Nanotechnology, 2006, 17, 3933.
  • Use of NaBr has been disclosed in, for example, L.
  • Japanese patent application publication 2009-155674 discloses use of SnCl 4 .
  • U.S. patent application publication 2010/0148132 discloses use of NaCl, KC1, CaCl 2 , MgCl 2 , and ZnCl 2 .
  • U.S. patent application publications 2008/0210052 and 2011/0048170 disclose use of quaternary ammonium chlorides.
  • At least a first embodiment provides methods comprising providing at least one compound capable of forming at least one halide ion, where the compound comprises at least one first atom, at least one halogen atom bonded to the at least one first atom, and at least one carbon atom bonded to the at least one first atom; and reducing at least one first metal ion to at least one first metal in the presence of at least one of the at least one compound or the at least one halide ion.
  • the absolute value of the difference in electronegativities of the at least one first atom and the at least one halogen atom may be greater than about 0.4 Pauling units and less than about 2.0 Pauling units and the reducing is carried out in the absence of any metal ion differing in atomic number from that of the at least one first metal ion.
  • the at least one first atom may, for example, comprise at least one of a boron atom, a nitrogen atom, a phosphorus atom, a silicon atom, a sulfur atom, a selenium atom, or a carbon atom. Or, in some cases, the at least one first atom may comprise at least one of a boron atom, a
  • the at least one halide ion may, for example, comprise at least one chloride ion, bromide ion, or iodide ion. Or, in some cases, the at least one halide may comprise at least one chloride ion or bromide ion.
  • the at least one compound may comprise at least one carbocation.
  • a carbocation may be a primary carbocation, a secondary carbocation or a tertiary carbocation.
  • Non-limiting examples of the at least one compound are
  • diethyldichlorosilane diethyldichlorosilane, phenylphosphonic dichloride, dichlorophenylborane, and triphenylchloromethane .
  • such methods may further comprise forming the at least one first halide ion by solvolysis of the at least one compound.
  • Solvolysis may, for example, comprise one or more of hydrolysis, alcoholysis, glycolysis, acidolysis, aminolysis, or ammonolysis.
  • the at least one first metal may, for example, comprise at least one element from IUPAC Group 11 or at least one coinage metal.
  • An exemplary at least one first metal is silver.
  • inventions provide the at least one first metal produced by such methods. Still other embodiments provide nanowires comprising the at least one first metal produced by such methods.
  • At least a second embodiment provides methods comprising providing a composition comprising an amount of at least one organosilicon halide compound that is capable of forming at least one halide ion; and reducing at least one first metal ion to at least one first metal in the presence of the
  • the at least one organosilicon halide compound may, for example, comprise at least one silicon atom bonded to at least one halogen atom, or at least one silicon atom bonded to at least two halogen atoms.
  • the at least one halide ion may, for example, comprise at least one chloride ion.
  • the at least one first silver metal ion may, for example, comprise at least one element from IUPAC Group 11, or at least one coinage metal ion, or at least one silver ion.
  • the at least one organosilicon halide compound may, for example, comprise at least one silicon atom bonded to at least one halogen atom, or at least one silicon atom bonded to at least two halogen atoms.
  • the at least one halide ion may, for example, comprise at least one chloride ion.
  • the at least one first silver metal ion may, for example, comprise at least one element from IUPAC Group 11, or at least one coinage metal ion
  • organosilicon halide compound may, for example, comprise a silicon atom bonded to at least one halogen atom, where the silicon atom is also bonded to at least one carbon atom, or it may comprise a silicon atom bonded to at least one halogen atom, where the silicon atom is also bonded to at least two carbon atoms, or it may, for example, comprise diethyldichlorosilane.
  • such methods further comprise regulating the rate of halide generation by at least one of choosing the at least one organosilicon halide compound, selecting the amount of the at least one organosilicon halide compound in the composition, or selecting at least one temperature at which to perform the reduction.
  • inventions further provide the at least one first metal product produced according to such embodiments.
  • Such products may, for example, comprise at least one nanowire.
  • Still other embodiments further provide articles comprising the at least one first metal product produced according to such embodiments. Such articles may, for example, comprise electronic devices.
  • At least a third embodiment provides methods comprising providing a composition comprising at least one compound capable of forming at least one halide ion, where the compound comprises at least one of a boron atom, a nitrogen atom, a phosphorus atom, a sulfur atom, or a selenium atom; and reducing at least one first metal ion to at least one first metal ion the presence of the composition, where the reducing is carried out in the absence of any metal ion differing in atomic number from that of the at least one first metal ion.
  • the compound may, for example, comprise at least one first atom bonded to at least one halogen atom and to at least one carbon atom.
  • Such a first atom may, for example, comprise at least one of a boron atom, a nitrogen atom, a phosphorus atom, a sulfur atom, or a selenium atom.
  • An exemplary at least one compound is phenylphosphonic dichloride.
  • the at least one halide ion comprises at least one chloride ion.
  • the at least one first metal ion may, for example, comprise at least one element from IUPAC Group 11, or at least one coinage metal ion, such as, for example, a silver ion.
  • such methods may further comprise regulating the rate of halide generation by at least one of choosing the at least one compound, selecting the amount of the at least one compound in the composition, or selecting at least one temperature at which to perform the reduction.
  • the reducing may occur in the presence of at least one second metal or metal ion that has an atomic number different from that of the at least one first metal ion.
  • Such a product may, for example, comprise at least one nanowire.
  • Still other embodiments provide an article comprising the at least one first metal product produced by such methods.
  • At least a fourth embodiment comprises methods comprising providing an amount of at least one organo-halide compound, where the compound is capable of forming at least one carbocation and at least one halide ion and reducing the at least one first metal ion to at least one first metal in the presence of the composition, where the reducing is carried out in the absence of any metal ion differing in atomic number from that of the at least one first metal ion.
  • the at least one organo-halide compound may comprise a carbon atom bonded to at least one halogen atom, and also to at least one aromatic ring by at least one carbon-carbon bond. Or such a carbon atom may be bonded to at least one halogen atom, and also to at least two aromatic rings by at least two carbon-carbon bonds. Or such a carbon atom may be bonded to one halogen atom, and also to three aromatic rings by at three carbon-carbon bonds.
  • Such a compound may, for example, comprise
  • the at least one carbocation comprises at least one secondary carbocation or tertiary carbocation, or the at least one carbocation comprises at least one tertiary carbocation.
  • the at least one halide ion comprises a chloride ion or a bromide ion, or the at least one halide ion comprises at least one chloride ion.
  • such methods may further comprise regulating the rate of halide generation by at least one of choosing the at least one organo-halide compound, selecting the amount of the at least one organo-halide compound in the composition, or selecting at least one temperature at which to perform the reduction.
  • Such a product may, for example, comprise at least one nanowire.
  • FIG. 1 shows an optical micrograph of the silver nanowire product of Example 1.
  • FIG. 2 shows an optical micrograph of the silver nanowire product of Example 2.
  • FIG. 3 shows an optical micrograph of the silver nanowire product of Example 3.
  • FIG. 4 shows an optical micrograph of the silver nanowire product of Example 4.
  • FIG. 5 shows an optical micrograph of the reaction product of comparative Example 8.
  • FIG. 6 shows an optical micrograph of the reaction product of comparative Example 9.
  • FIG. 7 shows an optical micrograph of the reaction product of comparative Example 10.
  • FIG. 8 shows an optical micrograph of the reaction product of comparative Example 12.
  • FIG. 9 shows an optical micrograph of the reaction product of comparative Example 13.
  • FIG. 10 shows an optical micrograph of the reaction product of comparative Example 14.
  • FIG. 11 shows an optical micrograph of the silver nanowire product of Example 15.
  • FIG. 12 shows an optical micrograph of the silver nanowire product of Example 16.
  • FIG. 13 shows an optical micrograph of the silver nanowire product of Example 17.
  • FIG. 14 shows an optical micrograph of the silver nanowire product of Example 18.
  • FIG. 15 shows an optical micrograph of the silver nanowire product of Example 19.
  • 61/488,814 filed May 23, 2011, entitled NANOWIRE PREPARATION METHODS, COMPOSITIONS, AND ARTICLES; and U.S. Provisional Application No. 61/500,155, filed June 23, 2011, entitled NANOWIRE PREPARATION METHODS, COMPOSITIONS, AND ARTICLES, are each hereby incorporated by reference in its entirety.
  • At least some embodiments provide methods employing at least one compound capable of forming at least one halide ion in the reduction of metal ions, where the reduction occurs in the presence of the at least one compound or the at least one halide ion.
  • Such compounds comprise at least one first atom bonded to at least one carbon atom and to at least one halogen atom.
  • the bond between the at least one first atom and the at least one halogen atom may be termed a "polar covalent" bond, which for this application is meant in the sense that the absolute value of the difference in electronegativities of the at least one first atom and the at least one halogen atom is greater than about 0.4 Pauling units and less than about 2.0 Pauling units.
  • Such methods can allow production of, for example, metal nanowires that have reproducibly uniform thicknesses and lengths, even in the presence of run-to-run variability in the concentration of the at least one compound.
  • Some embodiments provide methods comprising reducing metal ions to metal.
  • metal ions may be referred to as "reducible metal ions," in the sense that that are capable of being reduced to a metal under some set of reaction conditions.
  • the metal ion may, for example, comprise at least one ion of an IUPAC Group 11 element or at least one coinage metal ion.
  • a coinage metal ion is an ion of one or more of the coinage metals, which include copper, silver, and gold.
  • Such metal ions may, in some cases, be provided as salts.
  • silver cations might, for example, be provided as silver nitrate.
  • the at least one metal is that metal to which the at least one metal ion is capable of being reduced.
  • silver would be the metal to which a silver cation would be capable of being reduced.
  • Some embodiments provide methods comprising reducing metal ions to metal in the presence of at least one compound or halide ion, where the compound comprises at least one first atom bonded to at least one carbon atom and to at least one halogen atom, where the bond between the at least one first atom and the at least one halogen atom is a "polar covalent" bond, which for this application is meant in the sense that the absolute value of the difference in electronegativities of the at least one first atom and the at least one halogen atom is greater than about 0.4 Pauling units and less than about 2.0 Pauling units.
  • the reducing is carried out in the absence of any metal ion differing in atomic number from that of the at least one first metal ion.
  • Such a reduction is carried out in the absence of ions of alkali metals, alkaline earth metals, transition metals, post-transition metals, main group metals, and rare earth metals.
  • Use of such compounds in the reduction of metal ions can allow the provision of halide ions without also providing catalyst metal cations or other nonprotic cations.
  • halide ions are provided with catalyst metal cations or other nonprotic cations in stoichiometric ratios governed by the identity of the halogen-bearing compounds. While not wishing to be bound by theory, it is believed that the presence of such cations can affect both the ability to form nanowires and the morphology of the nanowires that are formed.
  • the methods and compositions of this application can instead provide metal nanowires that have reproducibly uniform thicknesses and lengths, even in the presence of run-to-run variability in the concentration of the at least one compound.
  • the at least one first atom may, for example, comprise at least one of a boron atom, a nitrogen atom, a phosphorus atom, a silicon atom, a sulfur atom, a selenium atom, or a carbon atom. Or, in some cases, the at least one first atom may comprise at least one of a boron atom, a
  • the at least one halide ion may, for example, comprise at least one chloride ion, bromide ion, or iodide ion. Or, in some cases, the at least one halide may comprise at least one chloride ion or bromide ion.
  • Non-limiting examples of the at least one compound are diethyldichlorosilane, phenylphosphonic dichloride, dichlorophenylborane, and triphenylchloromethane .
  • X represents a halogen atom and R represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.
  • Substituted alkyl or aryl groups may comprise halogens, alkoxy moieties, amines, and the like.
  • the at least one compound may be capable of forming at least one carbocation and at least one halide ion.
  • Such a compound may, for example, comprise a carbon atom bonded to at least one halogen atom, and also to at least one aromatic ring by at least one carbon-carbon bond.; or the compound may, for example, comprise a carbon atom bonded to at least one halogen atom, and also to at least two aromatic rings by at least two carbon-carbon bonds; or the compound may, for example, comprise a carbon atom bonded to one halogen atom, and also to three aromatic rings by at three carbon- carbon bonds.
  • such a carbocation may comprise at least one secondary carbocation or tertiary carbocation, or the at least one carbocation comprises at least one tertiary carbocation.
  • Such a compound may, for example, comprise triphenylchloromethane.
  • such methods may further comprise forming the at least one first halide ion by solvolysis of the at least one compound.
  • Solvolysis is a type of nucleophilic substitution where the nucleophile is a solvent molecule.
  • Solvolyis may, for example, comprise one or more of hydrolysis, alcoholysis, glycolysis, acidolysis, aminolysis, or ammonolysis.
  • solvolysis may be performed in a reaction mixture that may, for example, comprise one or more polyols, such as, for example, ethylene glycol, propylene glycol, butanediol, glycerol, sugars, carbohydrates, and the like.
  • polyols such as, for example, ethylene glycol, propylene glycol, butanediol, glycerol, sugars, carbohydrates, and the like.
  • Solvolysis of the at least one compound can provide halide ions without simultaneously introducing catalyst metal ions or other nonprotic cations. Without wishing to be bound by theory, it is believed that solvolysis of the polar covalent bond between the at least one first atom and at least one halogen atom results in production of a halide ion and a proton or protic cation.
  • the metal product formed by such methods is a nanostructure, such as, for example, a one-dimensional nano structure.
  • Nanostructures are structures having at least one "nanoscale” dimension less than 300 nm. Examples of such nanostructures are nanorods, nanowires, nanotubes, nanopyramids, nanoprisms, nanoplates, and the like. "One-dimensional" nanostructures have one dimension that is much larger than the other two nanoscale dimensions, such as, for example, at least about 10 or at least about 100 or at least about 200 or at least about 1000 times larger.
  • Nanowires are one-dimensional nanostructures in which the two short dimensions (the thickness dimensions) are less than 300 nm, preferably less than 100 nm, while the third dimension (the length dimension) is greater than 1 micron, preferably greater than 10 microns, and the aspect ratio (ratio of the length dimension to the larger of the two thickness dimensions) is greater than five. Nanowires are being employed as conductors in electronic devices or as elements in optical devices, among other possible uses. Silver nanowires are preferred in some such applications.
  • Nanowires and other nanostructure products may be incorporated into articles, such as, for example, electronic displays, touch screens, portable telephones, cellular telephones, computer displays, laptop computers, tablet computers, point-of-purchase kiosks, music players, televisions, electronic games, electronic book readers, transparent electrodes, solar cells, light emitting diodes, other electronic devices, medical imaging devices, medical imaging media, and the like.
  • a common method of preparing nanostructures, such as, for example, nanowires, is the "polyol" process. Such a process is described in, for example, Angew. Chem. Int. Ed. 2009, 48, 60, Y. Xia, Y. Xiong, B. Lim,
  • Such processes typically reduce a metal cation, such as, for example, a silver cation, to the desired metal nanostructure product, such as, for example, a silver nanowire.
  • Such a reduction may be carried out in a reaction mixture that may, for example, comprise one or more polyols, such as, for example, ethylene glycol (EG), propylene glycol, butanediol, glycerol, sugars, carbohydrates, and the like; one or more protecting agents, such as, for example, polyvinylpyrrolidinone (also known as polyvinylpyrrolidone or PVP), other polar polymers or copolymers, surfactants, acids, and the like; and one or more metal ions.
  • polyols such as, for example, ethylene glycol (EG), propylene glycol, butanediol, glycerol, sugars, carbohydrates, and the like
  • protecting agents such as, for example, polyvinylpyrrolidinone (also known as polyvinylpyrrolidone or PVP), other polar polymers or copolymers, surfactants, acids, and the like
  • PVP polyvinylpyrrolidone
  • a method comprising:
  • composition comprising an amount of at least one
  • organosilicon halide compound capable of forming at least one halide ion
  • the at least one organosilicon halide compound comprises a silicon atom bonded to at least one halogen atom, said silicon atom being also bonded to at least one carbon atom.
  • K. The method according to embodiment A, wherein the at least one organosilicon halide compound comprises diethyldichlorosilane.
  • composition comprising at least one compound capable of forming at least one halide ion, said compound comprising at least one of a boron atom, a nitrogen atom, a phosphorus atom, a sulfur atom, or a selenium atom; and reducing at least one first metal ion to at least one first metal in the presence of the composition.
  • the at least one first atom comprises at least one of a boron atom, a nitrogen atom, a phosphorus atom, a sulfur atom, or a selenium atom.
  • regulating the rate of halide generation by at least one of choosing the at least one compound, selecting the amount of the at least one compound in the composition, or selecting at least one temperature at which to perform the reduction.
  • AD A method comprising:
  • At least one compound comprising at least one first atom and at least one second atom, said at least one first atom comprising at least one atom from IUPAC Group 13 and said at least one second atom comprising at least one halogen atom;
  • AN The method according to embodiment AD, wherein the compound comprises at least one boron-carbon bond and at least one boron-halogen bond.
  • AP The method according to embodiment AD, wherein the compound comprises dichlorophenylborane.
  • At least one article comprising the at least one first metal according to embodiment AS.
  • the at least one first metal comprises one or more nanowires, nanocubes, nanorods, nanopyramids, or nanotubes.
  • the article according to embodiment AT comprising at least one of an electronic display, a touch screen, a portable telephone, a cellular telephone, a computer display, a laptop computer, a tablet computer, a point-of-purchase kiosk, a music player, a television, an electronic game, an electronic book reader, a transparent electrode, a solar cell, a light emitting diode, an electronic device, a medical imaging device, or a medical imaging medium.
  • ARTICLES which is hereby incorporated by reference in its entirety, disclosed the following fourteen non-limiting exemplary embodiments:
  • a method comprising:
  • composition comprising an amount of at least one organo- halide compound, said compound capable of forming at least one carbocation and at least one halide ion;
  • the at least one organo-halide compound comprises a carbon atom bonded to at least one halogen atom, said carbon atom being also bonded to at least one aromatic ring by at least one carbon-carbon bond.
  • the at least one organo-halide compound comprises a carbon atom bonded to at least one halogen atom, said carbon atom being also bonded to at least two aromatic rings by at least two carbon-carbon bonds.
  • regulating the rate of halide generation by at least one of choosing the at least one organo-halide compound, selecting the amount of the at least one organo-halide compound in the composition, or selecting at least one temperature at which to perform the reduction.
  • An article comprising the at least one first metal product according to embodiment BH.
  • a method comprising:
  • At least one compound capable of forming at least one halide ion said compound comprising at least one first atom, at least one halogen atom bonded to the at least one first atom, and at least one carbon atom bonded to the at least one first atom;
  • the at least one first atom comprises at least one of a boron atom, a nitrogen atom, a phosphorus atom, a silicon atom, a sulfur atom, a selenium atom, or a carbon atom.
  • the at least one first atom comprises at least one of a boron atom, a phosphorus atom, a silicon atom, or a carbon atom.
  • the at least one compound comprises at least one of diethyldichlorosilane, phenylphosphonic dichloride, dichlorophenylborane, or triphenylmethylchloride.
  • the at least one first metal comprises at least one element from IUPAC Group 11 or at least one coinage metal.
  • BU The method according to embodiment BL, wherein the at least one first metal comprises silver.
  • BV At least one nanowire comprising the at least one first metal produced according to the method of embodiment BL.
  • a method comprising:
  • composition comprising a non-metal catalyst comprising silicon
  • non-metal catalyst comprises at least one silicon atom bonded to at least one carbon atom.
  • non-metal catalyst comprises at least one silicon atom bonded to at least two carbon atoms.
  • CE The method according to embodiment BW, wherein the at least one silicon atom is bonded to at least two hydrogen atoms.
  • the at least one non- metal catalyst comprises a silicon atom bonded to at least one halogen atom, said silicon atom being also bonded to at least one carbon atom.
  • the at least one non- metal catalyst comprises a silicon atom bonded to at least one halogen atom, said silicon atom being also bonded to at least two carbon atoms.
  • polyvinylpyrrolidinone (PVP, 55,000 weight- average molecular weight) in EG and 0.25 M AgN0 3 in EG were degassed with N 2 , then 20 mL syringes of each were prepared.
  • the reaction mixture was heated to 145 °C under N 2 , then the AgN0 3 and PVP solutions were added at a constant rate over 25 minutes via a 12 gauge Teflon syringe needle.
  • the reaction was held at 145 °C for 90 minutes then allowed to cool to ambient temperature.
  • Figure 3 shows an optical micrograph of the silver nanowire product.
  • the reaction mixture was heated to 145 °C under N 2 , then the AgN0 3 and PVP solutions were added at a constant rate over 25 minutes via a 12 gauge TEFLON ® fluoropolymer syringe needle. The reaction was held at 145 °C for 90 minutes then allowed to cool to ambient temperature.
  • the nanowires had an average diameter of 64.9 +16.5 nm and an average length of 15.5 + ⁇ , based on measurement of at least 100 wires.
  • Example 4 The procedure of Example 4 was repeated, varying the amount and concentration of the diethyldichlorosilane/EG catalyst solution used. The results are shown in Table I, along with the results of Example 4. The average diameters and lengths varied minimally over the range of catalyst solutions that were tested.
  • the reaction mixture was heated to 155 °C under N 2 and the AgN0 3 and PVP solutions were added at a constant rate over 25 minutes via 12 gauge TEFLON fluoropolymer syringe needles. The reaction was held at 155 °C for 90 minutes then allowed to cool to room temperature.
  • Figure 5 shows the reaction mixture after 60 min of reaction. Visible are nanoparticles, microparticles, with only a few short nanowires.
  • Example 8 The procedure of Example 8 was repeated, using 2.9 g of a freshly prepared 7.0 mM dispersion of K 2 IrCl6 in EG, instead of the IrCl 3 *3H 2 0 dispersion. The reaction was carried out at 145 °C, instead of 155 °C.
  • Figure 6 shows the reaction mixture after 90 min of reaction. Only a few fine nanowires are visible.
  • Example 8 The procedure of Example 8 was repeated, using 2.3 g of a freshly prepared 7.0 mM dispersion of ⁇ 3 ⁇ 4 ⁇ 2 0 in EG, instead of the ⁇ 3 ⁇ 3 ⁇ 2 0 dispersion.
  • Figure 7 shows the reaction mixture after 90 min of reaction. No nanowires are visible.
  • Figure 8 shows an optical micrograph of the nanowire product, which had an average diameter of 253.5 + 133.0 nm and an average length of 8.7 + 5.5 ⁇ , based on measurement of 100 wires.
  • Example 12 The procedure of Example 12 was repeated using 6.9 mg of zirconium tetrachloride bis(tetrahydrofuran) adduct in place of the hafnium- containing adduct.
  • Figure 9 shows an optical micrograph of the silver nanowire product, which had an average diameter of 147.3 + 50.0 nm and an average length of 15.6 + 12.0 ⁇ , based on measurement of 100 wires.
  • Example 14 (Comparative) The procedure of Example 12 was repeated using 9.9 mg of tantalum (V) chloride.
  • Figure 10 shows an optical micrograph of the silver nanowire product, which had an average diameter of 215 + 119 nm and an average length of 10.6 + 6.5 ⁇ , based on measurement of 100 wires.
  • Example 15 The procedure of Example 15 was replicated, except for the use of 0.16 g of a freshly prepared 0.27 M solution of benzylchloride in EG in place of the triphenylchloromethane. Under these conditions, silver nanowires were observed to begin forming, however, irregularly- shaped silver nanowires then formed, which tended to agglomerate into clusters.
  • Example 17 The procedure of Example 17 was repeated using 2.5 g of the 81 mM solution of diethyldichlorosilane in EG, instead of the 1.0 g used above.
  • An optical microscope picture of the silver nanowire product is shown in Figure 14.
  • Example 17 The procedure of Example 17 was repeated using 5.0 g of the 81 mM solution of diethyldichlorosilane in EG, instead of the 1.0 g used above.
  • An optical microscope picture of the silver nanowire product is shown in Figure 15.

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Abstract

L'invention concerne des procédés de fabrication de nanofils métalliques, des compositions et des articles. De tels procédés permettent une fabrication de nanofils métalliques ayant un diamètre et une longueur uniformes de manière reproductible, même en présence d'une variation de concentration de catalyseur. De tels nanofils métalliques sont utiles pour des applications électroniques.
PCT/US2012/029322 2011-05-23 2012-03-16 Procédés de préparation de nanofils, compositions et articles WO2012161857A1 (fr)

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US13/326,356 US8613887B2 (en) 2011-01-14 2011-12-15 Nanowire preparation methods, compositions, and articles
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