WO2009005261A2 - Nanofil monocristallin en métal noble et son procédé de fabrication - Google Patents

Nanofil monocristallin en métal noble et son procédé de fabrication Download PDF

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Publication number
WO2009005261A2
WO2009005261A2 PCT/KR2008/003737 KR2008003737W WO2009005261A2 WO 2009005261 A2 WO2009005261 A2 WO 2009005261A2 KR 2008003737 W KR2008003737 W KR 2008003737W WO 2009005261 A2 WO2009005261 A2 WO 2009005261A2
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Prior art keywords
noble metal
single crystalline
nanowire
substrate
set forth
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PCT/KR2008/003737
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English (en)
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WO2009005261A3 (fr
WO2009005261A4 (fr
Inventor
Bongsoo Kim
Yeongdong Yoo
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Korea Advanced Institute Of Science And Technology
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Priority claimed from KR1020070065030A external-priority patent/KR100906503B1/ko
Priority claimed from KR1020080036360A external-priority patent/KR100952615B1/ko
Application filed by Korea Advanced Institute Of Science And Technology filed Critical Korea Advanced Institute Of Science And Technology
Priority to JP2010514626A priority Critical patent/JP5318866B2/ja
Priority to US12/667,118 priority patent/US20100233426A1/en
Publication of WO2009005261A2 publication Critical patent/WO2009005261A2/fr
Publication of WO2009005261A3 publication Critical patent/WO2009005261A3/fr
Publication of WO2009005261A4 publication Critical patent/WO2009005261A4/fr

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    • 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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • 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
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/007—Growth of 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
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/005—Growth of 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
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements

Definitions

  • the present invention relates to a method for fabricating noble metal nanowire by a vapor phase transport method using noble metal oxide, noble metal material or noble metal halide
  • single crystalline noble metal nanowire can be any crystalline noble metal nanowire.
  • Ag has excellent electric and thermal conductivities and shows highest surface enhanced Raman 0 scattering (SERS) in the visible region due to its optical property.
  • SERS Raman 0 scattering
  • the SERS phenomenon can be observed m case of Au.
  • SAM self -assembled monolayer
  • the noble metal nanowire can be very utilized as electric, magnetic or optical devices or sensors.
  • the noble metal nanowire had been synthesized in vapor phase.
  • Conventionally known method for synthesizing the noble metal nanowire includes mainly a liquid phase chemical method using a template, a surfactant and a capping agent and there has not yet been reported up to now a case in which the noble metal nanowire had been successfully fabricated using the vapor 0 phase without catalyst.
  • the liquid phase chemical method has disadvantages that it is difficult to control the shape of the noble metal nanowire, and the fabricated noble metal nanowire has lowered purity and is defective or multi -crystalline . Also, the fabrication method is more complex than the vapor phase synthetic method and thus is difficult to apply to mass production.
  • This nanowire is generally fabricated by what is known as bottom-up type synthetic method and the nanowire is grown in disordered position and direction
  • the present inventor suggest a method for fabricating a mass producible noble metal nanowire with high purity and high quality and, as an advanced form, a method capable of controlling the position and direction of the nanowire through 'A) accurate control for the growth of the noble metal nanowire, thereby providing a base for realizing a three-dimensional device through the noble metal nanowire with controlled orientation for arrangement with respect to a substrate
  • the synthetic method by vertical growth of the present invention will provide a basic S technology that is very important m fabrication of a three- dimensional memory.
  • An object of the present invention is to provide a high purity and high quality single crystalline noble metal nanowire having an orientation with a substrate using non- catalytic vapor phase transport method and a method for fabricating the same, and another object of the present
  • ! 1 invention is to provide a device or sensor provided with the single crystalline noble metal nanowire of the present invention.
  • the method for fabricating a single crystalline noble metal nanowire is characterized in that a precursor containing noble metal oxide, noble metal material or noble metal halide located at a front portion of a furnace and a semiconductive or nonconductive single crystalline substrate located at a o rear portion of the reactor furnace are heat treated in an inert gas flow atmosphere, thereby forming a single crystalline noble metal nanowire on the single crystalline substrate .
  • the method of the present invention is a method of
  • driving force for nucleation, driving force for growth, nucleation rate and growth rate of the metal 0 material is finally controlled on the upper portion of the single crystalline substrate by controlling independently a temperature of the front portion of the furnace and a temperature of the rear portion of the furnace and controlling the flow rate of the inert gas and the pressure in the heat treating furnace tube used in the heat treatment, it is possible to fabricate high quality single crystalline noble metal nanowire with no defect and good crystalinity which is reproducible and controllable of size and density on the 1 substrate of the single crystalline noble metal nanowire.
  • the subject matter of the present invention is to fabricate metal nanowire by the vapor phase transport method not using catalyst but using noble metal oxide, noble metal material or noble metal halide as a precursor, and the
  • the '0 most important condition for fabricating the nanowire with high quality, high purity and desirable shape is temperatures at the front and rear portions of furnace, flow rate of the inert gas and pressure upon the heat treatment.
  • metal nanowire may include noble metal oxide, noble metal material and metal halide.
  • the noble metal oxide is preferably selected from silver oxide, gold oxide and palladium oxide; the noble metal material is preferably selected from silver, gold and palladium; and the noble metal halide is preferably
  • noble metal fluoride selected from noble metal fluoride, noble metal chloride, noble metal bromide and noble metal iodide, more preferably selected from noble metal chloride, noble metal bromide and noble metal iodide and most preferably noble metal iodide.
  • the noble metal halide is preferably selected from gold halide, silver halide and palladium halide.
  • the gold halide is preferably selected from gold fluoride, gold chloride, gold bromide and gold iodide;
  • the silver halide is preferably selected from silver fluoride, silver chloride, silver bromide ) and silver iodide;
  • the palladium halide is preferably selected from palladium fluoride, palladium chloride, palladium bromide and palladium iodide.
  • the noble metal halide may include noble metal halide hydrate.
  • the precursor is preferably noble metal oxide or noble 1 Q metal material and more preferably noble metal oxide.
  • the precursor may further include transition metal material.
  • transition metal material may include Co, Fe, Mg, Mn, Cr, Zr, Cu, Zn, V, Ti, Nb and Y, and a mixture thereof. i r )
  • the temperatures and pressure upon the heat treatment and the flow rate of the inert gas may be changed independently of each other, but it is possible to obtain single crystalline noble metal nanowire with desirable quality and shape only when the three conditions are changed dependently of other A) conditions .
  • the most preferable single crystalline noble metal nanowire may be fabricated from combination of above three conditions .
  • the respective temperatures of the front portion of the furnace and the rear portion of the furnace should be determined according to physical properties such as melting point, evaporation point and evaporation energy of the precursor, the flow rate of the inert gas and pressure upon 5 the heat treatment, but it is preferred that the temperature of the front portion of furnace is maintained equal or higher than the temperature of the rear portion of the furnace, and the temperature difference by subtracting the temperature of the rear portion of the furnace from the temperature of the
  • 10 front portion of the furnace is 0 to 700 0 C.
  • the inert gas is flowed preferably in 100 to 600sccm from the front portion of the furnace to the rear portion of the furnace.
  • the inert gas is flowed preferably in 400 to
  • the precursor is noble metal halide
  • the inert gas is flowed preferably in 100 to 300sccm from the front portion of the furnace to the rear portion of furnace.
  • the pressure upon the heat treatment is preferably lower than atmospheric pressure, more preferably 2 to 50torr and most preferably 2 to 20torr.
  • the noble metal nanowire may be fabricated at a pressure similar to the atmospheric pressure.
  • the temperature of the furnace, the flow rate of the xnert gas and the pressure upon the heat treatment have influences on evaporation degree of the precursor, amount per hour of the evaporated precursor transported to the substrate, ") nucleation and growth rate of the ferromagnetic metal material on the substrate and surface energy, agglomeration degree and morphology of noble metal material (nanowire) produced on the substrate .
  • the noble metal nanowire With the most desirable quality and shape by vapor phase transport method using the precursor of the present invention.
  • a quality problem such as agglomeration, shape deformation and defect of the fabricated nanowire and a problem of obtaining a metal body having a shape of not the nanowire but particles or a rod.
  • Heat treatment time should be also determined accordingA'O to the aforementioned temperature, flow rate of the inert gas and pressure upon the heat treatment and is carried out preferably for 30 minutes to 2 hour.
  • the precursor evaporated by the inert gas is moved to the substrate to participate in nucleation and growth, and at the same time, mass transfer (mass transfer on a per atom or cluster basis) through vapor phase and substrate surface occurs between already formed noble metal materials, and Ostwald ripening occurs.
  • the present invention suggests use of 0 noble metal oxide, noble metal material or noble metal halide as a precursor and a vapor phase transport method capable of fabricating noble metal nanowire using the precursor. Therefore, the precursor usable in the fabrication method of the present invention includes all noble metal oxide, noble r ) metal material and noble metal halide, and all noble metal single crystalline nanowire can be fabricated using the precursor.
  • the noble metal oxide may include gold oxide, silver oxide, palladium oxide, platinum oxide, iridium oxide, osmium oxide, rhodium oxide and0 ruthenium oxide, and using the noble metal oxide, gold, silver, palladium, platinum, iridium, osmium, rhodium or ruthenium single crystalline nanowire can be fabricated.
  • the noble metal oxide of gold oxide, silver oxide, palladium oxide, platinum oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide may be an oxide having a stoichiometric ratio that is thermodynamically stable at atmospheric temperature and pressure, or may be a noble metal oxide not having the stable stoichiometric ratio, which is resulted from point defects due to the noble metal or point defects due to oxygen.
  • All semiconductive or nonconductive single crystalline substrates that are chemically/thermally stable m the aforementioned heat treatment condition can be used as the substrate, but it is preferred a single crystalline substrate selected from group 4 single crystal selected from silicon single crystal, germanium single crystal and silicon-germanium single crystal, groups 3-5 single crystal selected from gallium-arsenic single crystal, indium-phosphorus single crystal and gallium-phosphorus single crystal, groups 2-6 single crystal, groups 4-6 single crystal, sapphire single crystal and silicon dioxide single crystal.
  • the substrate acts simply to provide a space for forming the noble metal nanowire on the upper portion thereof, a multi-crystal of aforementioned single crystalline substrate material may be used if necessary.
  • the respective temperatures of the front portion of the furnace and the rear portion of the furnace should be determined according to physical properties such as melting point, evaporation point and evaporation energy of the noble metal oxide and noble metal material, when fabricating Ag single crystalline nanowire using silver oxide as the noble metal oxide, silver or silver halide, it is T) preferred that the temperature difference by subtracting the temperature of the rear portion of the furnace from the temperature of the front portion of the furnace is 250 to 650°C, the precursor (noble metal oxide) is maintained at 850 to
  • the temperature difference by subtracting the temperature of the rear portion of the furnace from the
  • temperature of the front portion of the furnace is 0 to 300 0 C, the precursor is maintained at 1000 to 1200°C and the single crystalline substrate is maintained at 900 to 1000 0 C.
  • the temperature difference by subtracting the temperature of the rear portion of the furnace from the temperature of the front portion of the furnace is 0 to 300°C, the precursor is maintained at 1000 to 1200°C and the single crystalline substrate is maintained at 900 to 1000 0 C,
  • the single crystalline noble metal nanowire is characterized m that it is fabricated under a non-catalytic condition using the precursor containing noble metal oxide, 1 O noble metal material or noble metal halide and thus has an orientation with the surface of the semiconductive or nonconductive single crystalline substrate.
  • the orientation means the direction of the major axis of the nanowire fabricated on the substrate with respect to the
  • the nanowire has characteristically vertical or horizontal orientation with the surface of the substrate.
  • the noble metal single crystalline nanowire is fabricated by heat treating the precursor located at the front portion of /0 the furnace and the single crystalline substrate located at the rear portion of the furnace in an inert gas flow atmosphere with a predetermined pressure, and the orientation is controlled by kinds of the precursor, kinds of the single crystalline substrate, surface direction of the single crystalline substrate, the heat treatment temperature, the flow rate of the inert gas, the pressure or combination thereof .
  • the noble metal nanowire having a specific orientation with the substrate is preferably fabricated in such a condition that the precursor is maintained at 1000 to 1200 0 C, the single crystalline substrate is maintained at 800 to HOO 0 C, the inert gas is flowed m 50 to 200sccm from the frontO portion of the furnace (precursor) to the rear portion of the furnace (single crystalline substrate) and the heat treatment is carried out at a pressure of 3 to 20 torr .
  • the precursor usable m the fabrication of the noble metal nanowire may include noble metal oxide, noble ") metal material and metal halide, and the noble metal single crystalline nanowire can be fabricated using them.
  • the noble metal oxide may include gold oxide, silver oxide, palladium oxide, platinum oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and gold, silver, palladium,0 platinum, iridium, osmium, rhodium or ruthenium single crystalline nanowire can be fabricated using the noble metal oxide.
  • the noble metal material may include gold, silver, palladium, platinum, iridium, osmium, rhodium and ruthenium.
  • the noble metal halide is preferably selected from noble metal fluoride, noble metal chloride, noble metal bromide and noble metal iodide, more preferably selected from noble metal chloride, noble metal bromide and noble metal xodide and most preferably noble metal chloride.
  • the noble metal of the noble metal halide is selected gold, silver, palladium, platinum, iridium, osmium, rhodium and ruthenium, and the noble metal halide includes noble metal halide hydrate.
  • the precursor is preferably noble metal oxide or noble metal material . It is preferred that the noble metal oxide is selected from gold oxide and palladium oxide, the noble metal material is selected from gold and palladium, and the noble metal halide is selected from gold halide and palladium halide.
  • the noble metal single crystalline nanowire has the same crystalline structure as noble metal bulk and has high purity and high crystalinity . Also, a plurality of the noble metal single crystalline nanowires is arranged in a specific array.
  • the single crystalline noble metal nanowire is grown vertically with respect to the surface of the single crystalline substrate and thus has a vertical orientation.
  • the noble metal single crystalline nanowire having the vertical orientation has the same crystalline structure as noble metal bulk and a faceted shape.
  • the faceted shape means that the surface is not constituted of all plane in the crystal and an inclination of a tangent line is discontinuously varied on a periphery of a specific section including the minor axis or major axis of the noble metal nanowire .
  • the vertically grown single crystalline noble metal nanowire is Au single crystalline nanowire and the Au single crystalline nanowire has a face centered cubic (FCC) structure.
  • FCC face centered cubic
  • the Au single crystalline nanowire has a faceted shape, and the inclination of the tangent line is discontinuously
  • the growth direction is ⁇ 110> and thus the Au single crystalline nanowire has an orientation in which the surface of the substrate and ⁇ 110> direction of the Au single crystalline nanowire are perpendicular to each other.
  • ⁇ 000l ⁇ surface of a sapphire single crystalline substrate and the ⁇ 110> direction of the Au single crystalline nanowire are perpendicular to each other.
  • the vertically grown single crystalline noble metal nanowire is Pd single crystalline nanowire and the Pd single 0 crystalline nanowire has a face centered cubic (FCC) structure.
  • the Pd single crystalline nanowire has a faceted shape, and the inclination of the tangent line is discontinuously varied on the periphery of the major axis section of the Pd single crystalline nanowire.
  • the growth direction is ⁇ 110> and thus the Pd single crystalline nanowire has an orientation in which the surface of the substrate and ⁇ 110> direction of the Pd single crystalline nanowire are perpendicular to each other.
  • ⁇ OOOl ⁇ surface of a sapphire single crystalline substrate and the ⁇ 110> direction of the Pd single crystalline nanowire are perpendicular to each other
  • the noble metal nanowire having a vertical orientation with the substrate is preferably fabricated in such a condition that the precursor is maintained at 1000 to 1200°C, the single crystalline substrate is maintained at 850 to 1100°C, the inert gas is flowed in 50 to 200sccm from the front portion of the furnace to the rear portion of the furnace at a pressure of 3 to 8 torr.
  • the noble metal single crystalline nanowire is grown horizontally parallel to the surface of the single crystalline substrate and thus has a horizontal orientation.
  • the single crystalline noble metal nanowire which is grown horizontally parallel to the surface of the substrate is Au single crystalline nanowire.
  • the Au single crystalline nanowire has a face centered cubic (FCC) structure and the surface of the substrate and ⁇ ll ⁇ or ⁇ ill ⁇ face of the Au nanowire are parallel to each other.
  • the single crystalline substrate is preferably a ⁇ 0001 ⁇ surface sapphire substrate and has an orientation in which the ⁇ 0001 ⁇ face of the substrate and the ⁇ HO ⁇ face of the Au nanowire are parallel to each other.
  • the single crystalline substrate is preferably a ⁇ 11-20 ⁇ surface sapphire substrate and has an orientation in which the ⁇ 11-20 ⁇ face of the substrate and the ⁇ ill ⁇ face of the Au nanowire are parallel to each other.
  • the single crystalline noble metal nanowire which is grown horizontally parallel to the surface of the substrate is Pd single crystalline nanowire, and the Pd single crystalline nanowire has a face centered cubic (FCC) structure.
  • the single crystalline substrate on which the Pd single crystalline nanowire is fabricated is preferably a ⁇ OOOl ⁇ surface sapphire substrate.
  • the noble metal nanowire having a horizontal orientation with the substrate is preferably fabricated in such a condition that the precursor is maintained at 1000 to 1200°C, the single crystalline substrate is maintained at 800 to 950°C, the inert gas is flowed in 50 to 200sccm from the front portion of the furnace to the rear portion of the furnace at a pressure of 15 to 20 torr.
  • the single crystalline substrate is group 4 single crystalline substrate; groups 3-5 single crystalline substrate; groups 2-6 single crystalline substrate; groups 4-6 single crystalline substrate; sapphire single crystalline substrate; silicon oxide single crystalline substrate; or a stacked substrate thereof, and preferably a sapphire single crystalline substrate.
  • the method for fabricating a single crystalline noble T) metal nanowire is characterized in that the single crystalline noble metal nanowire an orientation with the single crystalline substrate is fabricated by heat treating a precursor containing noble metal oxide, noble metal material or noble metal halide located at the front of the furnace and
  • the orientation means the direction of the major axis of the nanowire fabricated on the substrate with respect to the
  • surface of the substrate, and the major axis of the single crystalline noble metal nanowire has characteristically vertical or horizontal orientation with the surface of the substrate .
  • the orientation is controlled by kinds of the precursor, kinds of the single crystalline substrate, surface direction of the single crystalline substrate, the heat treatment temperature, the flow rate of the inert gas, the pressure or combination thereof.
  • the precursor usable in the fabrication of the noble metal nanowire may include noble metal oxide, noble metal material and metal halide, and the noble metal single crystalline nanowire can be fabricated using them.
  • the noble metal oxide may include gold oxide, silver oxide, palladium oxide, platinum oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and gold, silver, palladium, platinum, iridium, osmium, rhodium or ruthenium single crystalline nanowire can be fabricated using the noble metal
  • the noble metal material may include gold, silver, palladium, platinum, iridium, osmium, rhodium and ruthenium.
  • the noble metal halide is preferably selected from noble metal fluoride, noble metal chloride, noble metal bromide and noble metal iodide, more preferably selected from i) noble metal chloride, noble metal bromide and noble metal iodide and most preferably noble metal chloride.
  • the noble metal of the noble metal halide is selected gold, silver, palladium, platinum, iridium, osmium, rhodium and ruthenium, and the noble metal halide includes noble metal halide hydrate. 0
  • the precursor is preferably noble metal oxide or noble metal material .
  • the noble metal oxide is selected from gold oxide and palladium oxide
  • the noble metal material is selected from gold and palladium
  • the noble metal halide is selected from gold halide and palladium halide.
  • the single crystalline substrate is group 4 single crystalline substrate; groups 3-5 single crystalline substrate; groups 2-6 single crystalline substrate; groups 4-6 1 single crystalline substrate; sapphire single crystalline substrate; silicon oxide single crystalline substrate; or a stacked substrate thereof, and preferably a sapphire single crystalline substrate.
  • the single crystalline noble metal nanowire is grown vertically with respect to the surface of the single crystalline substrate. At this time, it is preferred that the precursor is maintained at 1000 to 1200 0 C, the single crystalline substrate is maintained at 850 to 1100 0 C, the inert
  • the single crystalline substrate on which the vertically growing single crystalline noble metal nanowire is fabricated is
  • the precursor is gold oxide or gold and the vertically growing single crystalline noble metal nanowire is Au single crystalline nanowire.
  • the precursor is palladium oxide or palladium and the vertically growing single crystalline noble metal nanowire is Pd single crystalline nanowire.
  • the single crystalline noble metal nanowire is
  • the precursor is maintained at 1000 to 1200 0 C
  • the single crystalline substrate is maintained at 800 to 950°C
  • the inert gas flows in 50 to 200sccm from the front portion of the
  • the single crystalline substrate on which the horizontally growing single crystalline noble metal nanowire is fabricated is preferably a sapphire substrate, and the
  • surface of the sapphire substrate is ⁇ 000l ⁇ face or ⁇ 11-20 ⁇ face .
  • the precursor is gold oxide or gold and the horizontally growing single crystalline noble metal nanowire is Au single crystalline nanowire.
  • O The precursor is palladium oxide or palladium and the horizontally growing single crystalline noble metal nanowire is Pd single crystalline nanowire.
  • the method for fabricating the single crystalline noble metal nanowire having an orientation with the substrate is characterized in that a precursor containing noble metal oxide, noble metal material or noble metal halide located at a front portion of a furnace and a semiconductive or nonconductive single crystalline substrate are heat treated in an inert gas flow atmosphere at a predetermined pressure, thereby forming a single crystalline noble metal nanowire having an orientation on the single crystalline substrate.
  • the precursor evaporated by the heat treatment is transferred by the flow of the inert gas to cause nucleation and growth of the noble metal on the surface of the single crystalline substrate, thereby forming the single crystalline noble metal nanowire having vertical or horizontal orientation with the surface of the single crystalline substrate .
  • the fabrication method of the present invention is a method of forming the noble metal nanowire on the single crystalline substrate not using catalyst but simply using the noble metal oxide, noble metal material or noble metal halide as a precursor, and has advantages that the process is simple and reproducible and high purity nanowire containing no impurities can be fabricated since the noble single crystalline metal nanowire is fabricated through a vapor phase mass transfer path without using catalyst.
  • fabrication method of the present invention has advantages that it is possible to fabricate the single crystalline noble metal nanowire having vertical or horizontal orientation with the surface of the substrate, being independent from each other without agglomeration and arrangedC) uniformly in a specific direction, by controlling the nucleation and growth.
  • the major axis of the single crystalline noble metal nanowire produced by nucleation and growth on the substrate has vertical or horizontal relationship with respect to the5 surface of the single crystalline substrate, and this vertical or horizontal orientation is controlled by kinds of the precursor, kinds of the single crystalline substrate, surface direction of the single crystalline substrate, the heat treatment temperature, the flow rate of the inert gas, the0 pressure or combination thereof.
  • the substrate is the surface of nonconductive or semiconductive single crystal on which U) nucleation, particularly two dimensional nucleation of the targeting noble metal single crystal is easily generated, and should be suitably selected so that elastic stress and dislocation due to lattice mismatch are not easily generated.
  • Two dimensional nucleation energy barrier of the noble '5 metal single crystal is determined by material of targeting single crystal noble metal nanowire, atomic structure of low index faces of the targeting single crystal noble metal nanowire, material of the single crystalline substrate, surface direction of the single crystalline substrate or a O combination thereof.
  • the nucleation and growth are varied as material of the single crystalline substrate, surface direction of the single crystalline substrate or a combination thereof and the orientation of the single crystalline noble metal nanowire with respect to the substrate may be finally controlled.
  • the semiconductive or nonconductive substrate is actually selected 0 from group 3 single crystal selected from silicon single crystal, germanium single crystal and silicon-germanium single crystal, groups 3-5 single crystal selected from gallium- arsenic single crystal, indium-phosphorus single crystal and gallium-phosphorus single crystal, groups 2-6 single crystal, T) groups 4-6 single crystal, sapphire single crystal and silicon dioxide single crystal, or a stacked substrate thereof.
  • the targeting single crystalline noble metal nanowire is Au or Pd single crystalline nanowire
  • a low cost sapphire single crystal is actually used, in which the 0 nucleation of the noble metal is easily generated on the low index surface which is a thermodynamically stable surface.
  • the noble metal nanowire having an orientation with the surface of the single crystalline substrate it is necessary to control initial n ⁇ cleation and growth step of the noble metal material.
  • the most important conditions for controlling the step are the pressure in the heat treatment tube, the heat treatment temperatures of the front portion of the furnace (precursor) I and the rear portion of the furnace (substrate) and flow rate of the inert gas.
  • the atoms on the surface have atomically rough structure.
  • an influence of broken bond energy according to crystal direction of the single crystal becomes larger than entropy energy and thus the single crystal comes to have a faceted shape.
  • Each face constituting the faceted shape is the O surface in the crystal direction of low surface energy and the surface is known to have atomically singular structure.
  • thermodynamic phase transformation has large influence of the nucleation and growth of the particle. Normal nucleation and growth occur when the atomic structure is a rough structure, but two dimensional nucleation and lateral growth occur when the atomic structure is a singular structure.
  • the arranged orientation is obtained by controlling the thermally stable surface phase of the noble metal material using the heat treatment temperature and pressure, and controlling nucleation and growth driving forces transferred to the substrate surface
  • the precursor is maintained at 1000 to 1200 0 C
  • the single crystalline substrate is maintained at 800 to 1100 0 C
  • the inert gas flows in 50 to 200sccm from the i 5 front portion of the furnace (precursor) to the rear portion of the furnace (single crystalline substrate), and the heat treatment is carried at a pressure of 3 to 30torr.
  • the precursor is maintained at 1000 to 1200 0 C
  • the single crystalline substrate is maintained at 850 to HOO 0 C
  • the inert gas flows in 50 to 200sccm from the front portion of the furnace (precursor) to the rear portion of the furnace (single crystalline substrate)
  • the heat treatment is carried at a pressure of 3 to 8torr.
  • the precursor is maintained at 1000 to 1200 0 C
  • the single crystalline substrate is maintained at 800 to 950 0 C
  • the inert gas flows in 50 to 200sccm from the front portion of the furnace (precursor) to the rear portion of the furnace (single crystalline substrate), and the heat treatment is carried at a pressure of 15 to 20torr.
  • Heat treatment time should be also determined according to the aforementioned temperature, flow rate of the inert gas and pressure upon the heat treatment and is carried out preferably for 30 minutes to 2 hour.
  • the precursor evaporated by the inert gas is moved to the substrate to participate in nucleation and growth, and at the same time, mass transfer of the noble metal material through vapor phase and substrate surface occurs between already formed noble metal materials, and particle growth occurs .
  • the precursor usable in the fabrication of the noble metal nanowire may include noble metal oxide, noble metal material and metal halide, and the noble metal single crystalline nanowire can be fabricated using them.
  • the noble metal oxide may include gold oxide, silver oxide, if) palladium oxide, platinum oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and gold, silver, palladium, platinum, iridium, osmium, rhodium or ruthenium single crystalline nanowire can be fabricated using the noble metal oxide.
  • the noble metal material may include gold, 0 silver, palladium, platinum, iridium, osmium, rhodium and ruthenium, and gold, silver, palladium, platinum, iridium, osmium, rhodium or ruthenium single crystalline nanowire can be fabricated using the noble metal material.
  • the noble metal halide is preferably selected from noble metal fluoride, noble metal chloride, noble metal bromide and noble metal iodide, more preferably selected from noble metal chloride, noble metal bromide and noble metal iodide and most preferably noble metal chloride.
  • the noble metal of the noble metal halide is selected gold, silver, palladium, platinum, iridium, osmium, rhodium and ruthenium, and the noble metal halide includes noble metal halide hydrate.
  • the precursor is preferably noble metal oxide or noble metal material.
  • the precursor may further include transition metal material.
  • transition metal material may include Co, Fe, Mg, Mn, Cr, Zr, Cu, Zn, V, Ti, Nb and Y, and a mixture thereof.
  • gold oxide gold or gold halide, preferably gold
  • the gold halide is preferably selected from gold fluoride, gold chloride, gold bromide and gold iodide
  • the palladium halide is preferably selected from palladium fluoride, palladium chloride, palladium bromide and palladium iodide .
  • Fig. 1 is a scanning electron microscope (SEM) image showing an Ag nanowire fabricated through Example 1 of the present invention.
  • Fig. 2 is a transmission electron microscope (TEM) image showing the Ag nanowire fabricated through Example 1 of the present invention.
  • Fig. 3 shows electronic diffraction patterns according to zone axes of the Ag nanowire fabricated through Example 1 of the present invention.
  • Fig. 4 is a high resolution TEM (HRTEM) image showing the Ag nanowire fabricated through Example 1 of the present invention .
  • Fig. 5 is an energy dispersive spectroscopy (EDS) result of the Ag nanowire fabricated through Example 1 of the present invention.
  • Fig. 6 is an X-ray diffraction (XRD) result of the Ag nanowire fabricated through Example 1 of the present invention.
  • Fig. 7 is a SEM image showing an Au nanowire fabricated through Example 2 of the present invention.
  • Fig. 8 is an XRD result of the Au nanowire fabricated through Example 2 of the present invention.
  • Fig. 9 is a TEM result of the Ag nanowire fabricated through Example 1 of the present invention, in which Fig 9a is a selected area electron diffraction pattern (SAED) of the Ag
  • H3 nanowire m Fig. 9b and Fig. 9b is a dark field image of the
  • Fig. 10 is an EDS result of the Au nanowire fabricated through Example 2 of the present invention.
  • Fig. 11 is a SEM image showing a Pd nanowire fabricated 11 through Example 3 of the present invention.
  • Fig. 12 is an XRD result of the Pd nanowire fabricated through Example 3 of the present invention.
  • Fig. 13 is a TEM result of the Pd nanowire fabricated through Example 3 of the present invention, in which Fig 13a ⁇ ) is a SAED of the Pd nanowire m Fig. 13b and Fig. 13b is a dark field image of the Pd nanowire.
  • Fig. 14 is an EDS result of the Pd nanowire fabricated through Example 3 of the present invention.
  • Fig. 15 is a SEM image showing a Pd nanowire fabricated through Example 4 of the present invention.
  • Fig. 16 is a TEM result of the Pd nanowire fabricated through Example 4 of the present invention, in which an image inserted in upper right portion of Fig. 16 is a SAED of the Pd nanowire m Fig. 16.
  • Fig. 17 is an EDS result of the Pd nanowire fabricated through Example 4 of the present invention.
  • Fig. 18 is a SEM image showing an Au nanowire fabricated through Example 5 of the present invention.
  • Fig. 19 is a high magnification SEM image showing the Au nanowire fabricated through Example 5 of the present invention.
  • Fig. 20 is a SEM image showing an Au nanowire fabricated through Example 6 of the present invention.
  • Fig. 21 is an XRD result of the Au nanowire fabricated through Example 6 of the present invention.
  • Fig. 22 is a TEM result of the Au nanowire fabricated through Example 6 of the present invention, in which Fig 22a is a SAED of the Au nanowire in Fig. 22b, Fig. 22b is a dark field image of the Au nanowire and Fig. 22c is a HRTEM of Fig. 22b.
  • Fig. 23 is an EDS result of the Au nanowire fabricated through Example 6 of the present invention.
  • Fig. 24 is a SEM image showing a Pd nanowire fabricated through Example 7 of the present invention.
  • Fig. 25 is an XRD result of the Pd nanowire fabricated through Example 7 of the present invention.
  • Fig. 26 is a TEM result of the Pd nanowire fabricated through Example 7 of the present invention, in which Fig 26a
  • Fig. 26b is a SAED of the Pd nanowire in Fig. 26b
  • Fig. 26b is a dark field image of the Pd nanowire
  • Fig. 26c is a HRTEM of Fig.
  • Fig. 27 is an EDS result of the Pd nanowire fabricated through Example 7 of the present invention.
  • Fig. 28 is a SEM image showing an Au nanowire fabricated through Example 8 of the present invention.
  • Fig. 29 is a HRTEM image showing an interface between the Au nanowire fabricated through Example 8 of the present invention and a substrate.
  • Fig. 30 is a SEM image showing an Au nanowire fabricated through Example 9 of the present invention.
  • Fig. 31 is a HRTEM image showing an interface between the Au nanowire fabricated through Example 9 of the present invention and a substrate.
  • FIG. 32 is a SEM image showing a Pd nanowire fabricated through Example 10 of the present invention.
  • Example 1 An Ag single crystalline nanowire was synthesized in a furnace using vapor phase transport method.
  • the furnace is divided into a front portion and a rear portion, which are independently provided with a heating element and a temperature controller.
  • a tube in the furnace was formed of quartz having a size of linch diameter and 60cm length .
  • Argon gas is inputted into the front portion of the furnace and discharged from the rear portion of the furnace, and the rear portion of the furnace is provided with a vacuum pump.
  • a pressure within the quartz tube was maintained at 15torr using the vacuum pump and Ar was allowed to flow in 500sccm by using a mass flow controller (MFC) .
  • MFC mass flow controller
  • a silicon wafer having (100) crystal face formed with a natural oxidation layer on the surface thereof was used as the silicon substrate.
  • Heat treatment was carried out for 30 minutes in a state that the temperature of the front portion of the furnace
  • substrate is maintained at 500°C, thereby fabricating Ag single crystalline nanowire.
  • the Au single crystalline nanowire was fabricated using the same condition and apparatus of Example 1, except for the precursor, the heat treatment temperature and the material of 1 I the single crystalline substrate.
  • Heat treatment was carried out for 30 minutes in a state 0 that the temperature of the front portion of the furnace
  • a Pd single crystalline nanowire was synthesized in a furnace using vapor phase transport method.
  • the Pd single crystalline nanowire was fabricated using T) the same condition and apparatus of Example 1, except for the precursor, the heat treatment temperature, the pressure and the material of the single crystalline substrate.
  • PdO Sigma-Aldrich, 203971
  • a (0001) surface sapphire single crystal 10 used as the single crystalline substrate.
  • the pressure in the quartz tube was maintained at 5torr using the vacuum pump.
  • Heat treatment was carried out for 30 minutes in a state that the temperature of the front portion of the furnace
  • a Pd 0 single crystalline nanowire was fabricated using palladium as the precursor (Example 4), and an Au single crystalline nanowire was fabricated using gold chloride as the precursor
  • a Pd single crystalline nanowire was synthesized in a furnace using vapor phase transport method.
  • the Pd single crystalline nanowire was fabricated using "> the same condition and apparatus of Example 3, except that 0.03g of Pd (Sigma-Aldrich, 203939) was used as the precursor.
  • An Au single crystalline nanowire was synthesized in a 0 furnace using vapor phase transport method.
  • the Au single crystalline nanowire was fabricated using the same condition and apparatus of Example 2, except for the precursor, the pressure and the flow rate of the inert gas.
  • Figs. 1 to 6 show results of measuring the Ag nanowire fabricated through Example 1.
  • Fig. 1 is a scannxng electron microscope (SEM) image showing the Ag nanowire fabricated through Example 1 of the present invention. As can be appreciated from Fig. 1, a large amount of nanowires was formed m uniform size of tens
  • U) nanowire is 80 to 150nm and a length of the major axis thereof is greater than lO ⁇ m.
  • Fig. 2 is a transmission electron microscope (TEM) image showing the Ag nanowire .
  • TEM transmission electron microscope
  • the section of the Ag single crystalline nanowire perpendicular to the growth direction has smoothly curved shape in which an inclination of the tangent line on the periphery of the section is continuously varied and the section has a circular
  • a section of a growth directional end of the Ag single crystalline nanowire has an elliptic shape with no faceted portion.
  • Fig. 3 shows SAED patterns with respect to 3 zone axis of the single Ag nanowire fabricated through Example 1 of the present invention. From the electronic diffraction patterns in Fig. 3, it can be appreciated that One Ag a nanowire is a single crystal body. From the a distance between a point of 1 the zone axis (a transmitting point) and a diffraction point and the results of the electronic diffraction pattern according to the zone axis m Fig. 3, it can be appreciated that the fabricated Ag nanowire has a face centered cubic (FCC) structure and has a size of the unit cell which is 10 identical to that of the bulk Ag.
  • FCC face centered cubic
  • Fig. 4 is a high resolution TEM (HRTEM) image showing the Ag nanowire.
  • HRTEM high resolution TEM
  • the surface constituting the major axis of the smoothly curved Ag nanowire has an atomically rough structure and the growth direction of i r ) the Ag nanowire is ⁇ 110> direction.
  • a space between (110) faces is 0.29nm which is identical to the bulk Ag.
  • Fig. 5 is a result of component analysis for the Ag nanowire using an energy dispersive spectroscopy (EDS) W) attached to the TEM equipment.
  • EDS energy dispersive spectroscopy
  • Fig. 6 is an X-ray diffraction (XRD) result of the Ag nanowire .
  • the diffraction result is exactly agreed with the diffraction result of the bulk Ag without peak shift, and the fabricated Ag nanowire has a FCC structure.
  • Figs. 7 to 10 show results of measuring the Au nanowire fabricated through Example 2.
  • Fig. 7 is a SEM image showing the Au nanowire fabricated on the sapphire single crystalline substrate.
  • Ag nanowire having a shape extending straightIy in a major axis direction of the nanowire and individually separable without agglomeration of the nanowires were formed, and a diameter of 1") minor axis of the Au single crystalline nanowire is 50 to 150nm and a length of the major axis thereof is greater than
  • Fig. 8 is an XRD (X-Ray Diffraction) result of the Au nanowire.
  • the diffraction result is exactly agreed with the v() diffraction result of the bulk Au without peak shift, and the fabricated Au nanowire has a FCC (Face Centered Cubic) structure .
  • the fabricated Au nanowire has a smooth surface and a section of a growth directional end of the Au single crystalline nanowire has a faceted shape unlike the Ag.
  • the 7> fabricated Au nanowire is a single crystal body formed of a single crystal
  • the growth direction (major axis) of the Au single crystalline nanowire is ⁇ 110> direction
  • each face forming the facet of the face faceted shaped nanowire is a low index face such as ⁇ ill ⁇ , ⁇ ll ⁇ and ⁇ l00 ⁇ .
  • 0 Fig. 10 is a result of component analysis for the Au nanowire using an EDS attached to the TEM equipment.
  • the fabricated nanowire is made of Au alone except for substance subordinately measured due to the characteristic of the
  • measuring equipment such as a grid.
  • Figs . 11 to 14 show results of measuring the Pd nanowire fabricated through Example 3.
  • Fig. 11 is a SEM image showing the Pd nanowire fabricated on the sapphire single crystalline O substrate.
  • Ag nanowire having a shape extending straightly in a major axis direction of the nanowire and individually separable without agglomeration of the nanowires were formed, and a diameter of minor axis of the Pd single crystalline nanowire is 50 to 150nm and a length of the major axis thereof is greater than 5 ⁇ m .
  • Fig. 12 is an XRD result of the Pd nanowire.
  • the diffraction result of the fabricated Pd nanowire is agreed with the diffraction result of the bulk Pd, and the fabricated Pd nanowire has a FCC structure.
  • the fabricated Pd nanowire has a smooth surface and a section of a growth directional end of the Au single crystalline nanowire has a faceted shape unlike the Ag.
  • the fabricated Pd nanowire is a single crystal body formed of a single crystal, the growth direction (major axis) of the Pd single crystalline nanowire is ⁇ 110> direction, and each face forming the facet of the face faceted shaped nanowire is a low index face such as ⁇ ill ⁇ , ⁇ ll ⁇ and ⁇ l00 ⁇ .
  • Fig. 14 is a result of component analysis for the Pd nanowire using an EDS attached to the TEM equipment.
  • the fabricated nanowire is made of Pd alone except for substance subordinately measured due to the characteristic of the measuring equipment such as a grid.
  • Figs. 15 to 17 show results of measuring the Pd nanowire fabricated through Example 4.
  • Fig. 15 is a SEM image showing the Pd nanowire fabricated on the sapphire single crystalline substrate using a Pd precursor.
  • a Pd precursor palladium oxide as a precursor
  • the fabrication result using palladium oxide as a precursor it can be appreciated that a large amount of nanowires was formed in a size of several micrometer separably from the sapphire single crystalline substrate, and Pd nanowire having a shape extending straightly in a major axis direction of the nanowire and individually separable without agglomeration of the nanowires were formed.
  • the fabricated Pd nanowire has a smooth surface.
  • SAED shown at upper left in Fig.
  • the fabricated Pd nanowire is a single crystal body formed of a single crystal and the growth direction (major axis) of the Pd single crystalline nanowire is ⁇ 110> direction.
  • Fig. 17 is a result of component analysis for the Pd nanowire using an EDS attached to the TEM equipment. As can be appreciated from the result of Fig. 17, the fabricated nanowire is made of Pd alone except for substance subordinately measured due to the characteristic of the measuring equipment such as a grid.
  • Figs. 18 and 19 show results of measuring the Au nanowire fabricated through Example 5.
  • Fig. 18 is a SEM image showing the Au nanowire fabricated on the sapphire single crystalline substrate using AuCl as the precursor and
  • Fig. 19 is a high magnification SEM image. It can be appreciated that also when using AuCl as the precursor, a large amount of nanowires was formed in a size of several micrometer separably from the sapphire single crystalline substrate, and Au nanowire having a shape extending straightIy in a major axis direction of the nanowire and individually separable without agglomeration of the nanowires were formed.
  • the furnace is divided into a front portion and a rear portion, which are independently provided with a heating element and a temperature controller.
  • a tube in the furnace was formed of quartz having a size of linch diameter and 60cm length .
  • Argon gas is inputted into the front portion of the furnace and discharged from the rear portion of the furnace, and the rear portion of the furnace is provided with a vacuum pump.
  • a pressure within the quartz tube was maintained at 5torr using the vacuum pump and Ar was allowed to flow in lOOsccm by using a MFC.
  • Heat treatment was carried out for 30 minutes in a state that the temperature of the front portion of the furnace
  • a Pd single crystalline nanowire vertically oriented with the substrate was synthesized in a furnace using vapor phase transport method.
  • the Pd nanowire was fabricated using the same condition and apparatus of Example 6, except for the heat treatment temperature, the precursor, the flow rate of the inert gas and the pressure.
  • PdO Sigma-Aldrich, 203971
  • the pressure in the quartz tube was maintained at 6torr using the vacuum pump.
  • Heat treatment was carried out for 30 minutes in a state that Ar flows in BOOsccm, the temperature of the front portion of the furnace (alumina boat containing the precursor) is maintained at 1100 0 C and the temperature of the rear portion of the furnace (sapphire substrate) is maintained at 900 0 C, thereby fabricating Pd single crystalline nanowire .
  • the Au single crystalline nanowire was fabricated using the same condition and apparatus of Example 6, except for the heat treatment temperature, the pressure and the flow rate of the inert gas .
  • the pressure in the quartz furnace was maintained at 17torr using the vacuum pump, and heat treatment was carried out for 30 minutes in a state that Ar flows in 80sccm, the temperature of the front portion of the furnace (alumina boat containing the precursor) is maintained at HOO 0 C and the temperature of the rear portion of the furnace (sapphire substrate) is maintained at 850°C, thereby fabricating the Au single crystalline nanowire .
  • the Au single crystalline nanowire was fabricated using ]() the same condition and apparatus of Example 8, except for using a (11-20) face single crystalline sapphire substrate.
  • a Pd single crystalline nanowire horizontally oriented 15 with the substrate was synthesized in a furnace using vapor phase transport method.
  • the Pd single crystalline nanowire was fabricated using the same condition and apparatus of Example 7, except for the heat treatment temperature, the pressure and the flow rate of 20 the inert gas .
  • the pressure in the quartz tube was maintained at 20torr using the vacuum pump, and heat treatment was carried out for 30 minutes in a state that Ar flows in lOOsccm, the temperature of the front portion of the furnace (alumina boat containing the precursor) is maintained at HOO 0 C and the temperature of the rear portion of the furnace (sapphire substrate) is maintained at 85O 0 C, thereby fabricating the Au single crystalline nanowire. 5
  • the Au single crystalline nanowire was fabricated using 10 the same condition and apparatus of Example 6, except for using 0.02g of Au as the precursor.
  • a Pd single crystalline nanowire vertically oriented with !T) the substrate was synthesized using Pd as the precursor.
  • the Pd single crystalline nanowire was fabricated using the same condition and apparatus of Example 7, except for using 0.05g of Pd as the precursor. 0 (Example 13)
  • the Au single crystalline nanowire was fabricated using the same condition and apparatus of Example 8, except for using Au as the precursor.
  • a Pd single crystalline nanowire horizontally oriented 1 with the substrate was synthesized using Pd as the precursor.
  • the Pd single crystalline nanowire was fabricated using the same condition and apparatus of Example 10, except for using Pd as the precursor.
  • Example 6 are similar to that of the nanowire fabricated in Example 11; physical properties of the nanowire fabricated in Example
  • Figs. 20 to 23 show results of measuring the Au nanowire fabricated through Example 6.
  • Fig. 20a is a SEM image showing Au nanowire fabricated on " " ) the sapphire single crystalline substrate. As can be appreciated from Fig. 20, the Au nanowire is grown and arranged vertically with respect to the surface of the single crystalline substrate. Also, it can be appreciated that a large amount of nanowires was formed and the Au nanowire
  • ⁇ Fig. 21 is an XRD result of the Au nanowire. It can be appreciated that the diffraction result is exactly agreed with the diffraction result of the bulk Au without peak shift and the fabricated Au nanowire has a FCC structure.
  • the fabricated Au nanowire has a smooth surface and a faceted shape.
  • the fabricated Au nanowire is a single crystal body formed of a single crystal.
  • the growth direction (major axis) of the Au single crystalline nanowire is ⁇ 110> direction.
  • the nanowire is a complete single crystal. From the results in Figs.
  • the section of the Au single crystalline nanowire perpendicular to the growth direction has a faceted shape in which inclination of the tangent line on the periphery of the section is discontinuously varied, and each face forming the faceted surface of the faceted shaped nanowire is a low index face such as ⁇ ill ⁇ , ⁇ ll ⁇ and ⁇ l00 ⁇ .
  • Fig. 23 is a result of component analysis for the Au nanowire using an EDS attached to the TEM equipment.
  • the fabricated nanowire is made of Au alone except for substance subordinately measured due to the characteristic of the measuring equipment such as a grid.
  • Figs. 24 to 27 show results of measuring the Pd nanowire fabricated through Example 7.
  • Fig. 24a is a SEM image showing Pd nanowire fabricated on the sapphire single crystalline substrate. It can be appreciated that a large amount of the nanowires having a diameter of 50 to 150nm and a length of 5 ⁇ 10 ⁇ m is grown and arranged vertically with respect to the surface of the single crystalline substrate. It can be appreciated that the Pd nanowire having a shape extending straight in a major axis direction and individually separable without agglomeration of the nanowires were formed. Also, through the high resolution SEM in Fig. 24b, it can be appreciated that the Pd nanowire has macroscopically a faceted shape.
  • Fig. 25 is an XRD result of the Pd nanowire. It can be appreciated that the diffraction result of the fabricated Pd nanowire is agreed with the diffraction result of the bulk Pd and the fabricated Pd nanowire has a FCC structure.
  • the fabricated Pd nanowire has a smooth surface and a faceted shape.
  • the fabricated Pd nanowire is a single crystal body formed of a single crystal, and the growth direction (major axis) of the Pd single crystalline nanowire is ⁇ 110> direction.
  • each face forming the faceted surface of the faceted shaped nanowire is a low index face such as ⁇ ill ⁇ , ⁇ 110 ⁇ and ⁇ l00 ⁇ .
  • the fabricated single crystalline nanowire is a low index face such as ⁇ ill ⁇ , ⁇ 110 ⁇ and ⁇ l00 ⁇ .
  • Fig. 27 is a result of component analysis for the Pd nanowire using an EDS attached to the TEM equipment.
  • the fabricated nanowire is made of Pd alone except for substance subordmately measured due to the characteristic of the measuring equipment such as a grid.
  • the noble metal nanowires of the present invention are, commonly and regardless of the material, a high purity nanowire which are grown and arranged vertically with respect to the surface of the single crystalline substrate, are high quality single crystal body and contain no impurities. Also, it can be appreciated that a large amount of nanowires are formed and respective nanowires are not agglomerated and are individually separable. Further, it can be appreciated that, m crystallographical characteristics, the single crystalline noble metal nanowire has the same crystalline structure as noble metal bulk and the single crystalline nanowire has a growth direction (major axis) of ⁇ 110> direction and a faceted shape.
  • Figs. 28 and 29 show results of measuring the Au nanowire fabricated through Example 8.
  • Fig. 28 is a SEM image showing Au nanowire fabricated on the sapphire single crystalline substrate. It can be appreciated that a large amount of the nanowires grown and arranged horizontally with respect to the surface of the single crystalline substrate is fabricated.
  • Fig. 29 is a HRTEM image showing an interface between the Au nanowire and the sapphire substrate.
  • the fabricated Au nanowire is formed of pure single crystal and has a FCC structure which is identical to the bulk
  • the Au single crystalline nanowire grown epitaxially on the surface of the sapphire single crystal has a growth direction of ⁇ 110> and the ma] or axis ( ⁇ 110>) of the Au nanowire is parallel to ⁇ ll-20> 0 direction of the surface of the sapphire single crystal. Accordingly, it can be appreciated that a plurality of Au nanowires horizontally grown as shown m Fig. 28 have a triangular or hexagonally arranged structure m six directions that are crystallographically identical to ⁇ ll-20>.
  • Figs. 30 and 31 show results of measuring the Au nanowire fabricated through Example 9.
  • Fig. 30 is a SEM image showing Au nanowire fabricated on the A- face sapphire single crystalline substrate. It can be O appreciated that a large amount of the nanowires grown and arranged horizontally with respect to the surface of the single crystalline substrate is fabricated. However, unlike Example 8 having a structure in which the major axis ( ⁇ 110>) of the Au nanowire is arranged in six directions
  • Fig. 31 is a HRTEM image showing an interface between the Au nanowire and the sapphire substrate. As can be appreciated from the electron diffraction pattern at upper right in Fig.
  • the fabricated Au nanowire is formed of pure single crystal and has a FCC structure which is identical to the bulk Au. Also, from the result of observation of crystallographic relationship between the fabricated Au nanowire and the substrate using TEM, it can be appreciated that, similarly to 0 Example 8, the Au single crystalline nanowire grown has a growth direction of ⁇ 110>, (11-1) face of the fabricated Au nanowire is epitaxial with (11-20) face, i.e. the surface of the sapphire single crystal and the major axis ( ⁇ 110>) of the Au nanowire is parallel to ⁇ 0001> direction of the A-face sapphire single crystal. Accordingly, it can be appreciated that a plurality of Au nanowires horizontally grown as shown in Fig. 30 is arranged in single direction of ⁇ 0001>.
  • Fig. 32 is a SEM image showing the PD nanowire fabricated through Example 10. Similarly to Au nanowires of Examples 8 and 9 that are grown parallel to the substrate, Pd nanowire ”) grown parallel to the substrate was fabricated. From the result of analysis for crystalline structure using TEM, it can be appreciated that single crystalline Pd nanowire was fabricated similarly to Example 7. Also, from the component analysis using EDS attached to TEM equipment, it can beO appreciated that pure Pd nanowire made of Pd alone was fabricated .
  • Example 6 to 10 it can be appreciated that high quality and high purity noble metal nanowire, which is fabricated under non-catalytic condition using a precursor containing noble metal oxide, noble metal material or noble metal halide, is pure single crystal body and has few internal defect, is formed on the upper portion of the substrate with a > predetermined orientation. Also, it can be appreciated that this orientation is controlled by kinds of the precursor, kinds of the single crystalline substrate, the surface direction of the single crystalline substrate, the heat treatment temperature, the flow rate of the inert gas, the) pressure or a combination thereof.
  • the method for fabricating a noble metal nanowire of the present invention and the noble metal nanowire fabricated by the fabrication method of the present invention it is possible to control the orientation with the surface of the substrate and size and shape of the nanowire; it is possible to provide a base for studying physical, optical and electromagnetic properties of the nanowire itself by providing a large amount of high purity and high quality nanowire through reproducible and simple process; and it is possible to enhance properties of electric devices, optical devices or magnetic devices and reduce the size thereof using the noble metal nanowire chemically stable and having excellent electric and thermal conductivities among metals.
  • a spectrometer using surface properties of the noble metal nanowire, a bio sensor, a sensor for detecting light, electricity, heat, vibration or combination thereof and it is thus possible to control detection properties and 1 enhance sensitivity, accuracy and reproducibility of the sensor.
  • it can be utilized as a MEMS structural body and a three dimensional memory device using vertical arrangement with respect to the surface of the single crystalline substrate .
  • the method of the present invention Since it is possible to fabricate a noble metal nanowire using non-catalytic vapor phase transport method, the method of the present invention has advantages that the process is 0 simple and reproducible, the fabricated nanowire is a defect free and impurity free, high quality and high purity noble metal nanowire of complete single crystal state, and it is possible to mass produce noble metal nanowire having uniform size and not agglomerated on the single crystalline substrate. Also, the method of the present invention has an advantage that it is possible to fabricate so that the single crystalline substrate and the fabricated noble metal nanowire have a specific orientation with each other.
  • the noble metal nanowire can be massively provided using controllable, reproducible and simple fabrication process, it is possible to provide a base for studying physical, optical and electromagnetic properties of the nanowire itself. Since it is possible to provide high purity i ⁇ and high quality Ag nanowire, Au nanowire and Pd nanowire chemically stable and having excellent electric and thermal conductivities among metals, it is possible to utilize them in a high sensitive, high efficient electric devices, optical devices or magnetic devices, particularly in a spectrometer
  • the noble metal nanowire having a specific orientation with the substrate can be massively provided using 0 controllable, reproducible and simple fabrication process, it is possible to provide a base for studying physical, optical and electromagnetic properties of the nanowire itself. Since it is possible to provide high purity and high quality Ag nanowire, Au nanowire and Pd nanowire chemically stable and having excellent electric and thermal conductivities among metals, it is possible to utilize them in a high sensitive, high efficient electric devices, optical devices or magnetic devices. Particularly, it is possible to utilize effectively the noble metal nanowire having an orientation with the surface of the substrate in a three dimensional MEMS structural body or a three dimensional memory device.

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Abstract

Procédé de fabrication d'un nanofil en métal noble monocristallin faisant intervenir un oxyde de métal noble, un matériau en métal noble ou un halogénure de métal noble en tant que précurseur et un nanofil en métal noble monocristallin, et plus particulièrement un procédé de fabrication d'un nanofil en métal noble monocristallin sur un substrat monocristallin par traitement thermique d'un précurseur disposé sur la partie avant d'un four et d'un substrat disposé sur la partie arrière d'un four dans une atmosphère à flux inerte, et un nanofil en métal noble monocristallin obtenu par ce procédé de fabrication. La fabrication du nanofil de l'invention fait appel à un procédé de transport en phase vapeur non catalytique. Le nanofil ainsi obtenu par ce processus simple et reproductible est exempt de défaut et d'impuretés. D'une qualité et d'une pureté élevées, ce nanofil en métal noble est monocristallin dans son intégralité.
PCT/KR2008/003737 2007-06-29 2008-06-27 Nanofil monocristallin en métal noble et son procédé de fabrication WO2009005261A2 (fr)

Priority Applications (2)

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JP2010514626A JP5318866B2 (ja) 2007-06-29 2008-06-27 貴金属単結晶ナノワイヤ及びその製造方法
US12/667,118 US20100233426A1 (en) 2007-06-29 2008-06-27 Noble metal single crystalline nanowire and the fabrication method thereof

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KR10-2007-0065030 2007-06-29
KR10-2007-0064993 2007-06-29
KR1020070065030A KR100906503B1 (ko) 2007-06-29 2007-06-29 귀금속 단결정 나노와이어 및 그 제조방법
KR20070064993 2007-06-29
KR10-2008-0036360 2008-04-18
KR1020080036360A KR100952615B1 (ko) 2007-06-29 2008-04-18 방향성을 갖는 귀금속 단결정 나노와이어 및 그 제조방법

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JP2010255093A (ja) * 2009-04-23 2010-11-11 Korea Advanced Inst Of Science & Technol 単結晶ツインフリー貴金属ナノワイヤ及びハロゲン化貴金属を利用した単結晶ツインフリー貴金属ナノワイヤの製造方法
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US20110121434A1 (en) * 2008-04-27 2011-05-26 Xiuling Li Method of fabricating a planar semiconductor nanowire
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JP2010255093A (ja) * 2009-04-23 2010-11-11 Korea Advanced Inst Of Science & Technol 単結晶ツインフリー貴金属ナノワイヤ及びハロゲン化貴金属を利用した単結晶ツインフリー貴金属ナノワイヤの製造方法

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