WO2005003409A1 - Procede de production d'un materiau de nanocarbone et procede de fabrication d'une structure filaire - Google Patents

Procede de production d'un materiau de nanocarbone et procede de fabrication d'une structure filaire Download PDF

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Publication number
WO2005003409A1
WO2005003409A1 PCT/JP2003/016831 JP0316831W WO2005003409A1 WO 2005003409 A1 WO2005003409 A1 WO 2005003409A1 JP 0316831 W JP0316831 W JP 0316831W WO 2005003409 A1 WO2005003409 A1 WO 2005003409A1
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Prior art keywords
catalyst metal
semiconductor
carbon
nanocarbon material
electrolysis
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PCT/JP2003/016831
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English (en)
Japanese (ja)
Inventor
Haruo Yokomichi
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Japan Science And Technology Agency
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Publication date
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Priority to US10/563,018 priority Critical patent/US20060163077A1/en
Priority to CA002530976A priority patent/CA2530976A1/fr
Publication of WO2005003409A1 publication Critical patent/WO2005003409A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes

Definitions

  • the present invention relates to a method for producing a nanocarbon material such as a carbon nanotube, and a method for producing a wiring structure using a nanocarbon material for wiring.
  • Nanocarbon materials such as so-called carbon nanotubes. Since these nanocarbon materials have different properties from the conventional carbon materials such as Graphite-Diamond, they are expected to be applied to electron emission sources for electrodes, conductive films, battery electrodes, and the like. Nanocarbon materials are also considered suitable for wiring applications.
  • a method for producing (synthesizing) the nanocarbon such as the carbon nanotubes described above a gas phase synthesis method and an arc discharge method are known.
  • DLC diamond-like carbon
  • carbon films have been studied as new carbon materials.
  • these DLCs and carbon films have been generally manufactured by vapor deposition (CVD, PVD), but recently, a manufacturing method by electrolytic deposition has been proposed (Hao Wang, et al. “Deposition of Diamond— ⁇ ike carbon ii ⁇ ms by electrolysis of methanol solution” ⁇ Deposition of Diamond— ⁇ ike carbon ii ⁇ ms by electrolysis of methanol solution Applied Physics Letters, August 19, 1969, 69 (8), ⁇ .
  • the present invention has been made to solve the above-described problems, and has as its object to provide a method for manufacturing a nanocarbon material and a method for manufacturing a wiring structure, which have a simple apparatus and can be manufactured at a low temperature. Disclosure of the invention
  • the present inventors have found that the use of a predetermined cathode and an electrolytic solution makes it possible to produce a nanocarbon material by electrolysis with a simpler apparatus and at a lower temperature (for example, room temperature) than before.
  • the method for producing a nanocarbon material of the present invention uses a semiconductor in which a catalyst metal is formed non-uniformly as a cathode and performs electrolysis in an electrolytic solution containing an organic solvent. A nanocarbon material is formed on the surface of the catalyst metal.
  • the method for producing a nanocarbon material of the present invention includes the steps of: electrolyzing a semiconductor in a electrolyte containing ions of a catalyst metal using a semiconductor as a cathode, and forming the catalyst metal unevenly on the surface of the semiconductor; Forming a nano-sized carbon material on the surface of the catalyst metal by subjecting the semiconductor in which the metal is formed non-uniformly to a cathode and performing electrolysis in an electrolytic solution containing an organic solvent. I do.
  • the method for producing a nanocarbon material according to the present invention includes the steps of: etching a catalyst metal formed on a surface of a semiconductor to form the catalyst metal non-uniformly on the surface of the semiconductor; Forming a nanocarbon material on the surface of the catalytic metal by electrolysis in an electrolyte containing an organic solvent using the formed semiconductor as a cathode.
  • the wiring structure is formed at both ends of a wiring forming position in a projecting shape.
  • the catalyst metal thus obtained is used as a cathode and a cathode or an anode, and is electrolyzed in an electrolytic solution containing an organic solvent to form a nanocarbon material as a wiring between the catalyst metals.
  • FIG. 1 is a diagram showing a configuration of an electrolysis apparatus suitable for use in producing the nanocarbon material of the present invention.
  • FIG. 2 is a diagram schematically showing a mode in which a nanocarbon material is electrodeposited.
  • FIG. 3 is another diagram schematically showing a mode in which the nanocarbon material is electrodeposited.
  • FIG. 4 (a) is a process drawing showing an aspect of performing the method of manufacturing a wiring structure of the present invention.
  • FIG. 4 (b) is a view following FIG. 4 (a).
  • FIG. 5 is another diagram showing an embodiment in which the method of manufacturing a wiring structure according to the present invention is performed.
  • FIG. 6 is a view showing an SEM image of a semiconductor substrate on which Ni is formed unevenly.
  • FIG. 7 is a diagram showing an SEM image of the substrate surface after electrodeposition.
  • FIG. 8 is a diagram showing a partially enlarged SEM image of FIG.
  • FIG. 9 is a diagram showing a partially enlarged SEM image of FIG.
  • FIG. 10 is a diagram showing a partially enlarged SEM image of FIG.
  • FIG. 11 is a diagram showing an SEM image of another place on the substrate surface after electrodeposition.
  • FIG. 12 is a diagram showing a partially enlarged SEM image of FIG. 11.
  • FIG. 13 is a diagram showing a TEM image of the deposit.
  • FIG. 14 is a diagram showing a TEM image of another measurement region of an electrodeposit.
  • FIG. 15 is a diagram showing a partially enlarged TEM image of FIG.
  • Figure 16 is a diagram showing an SEM image of another substrate surface after electrodeposition.
  • FIG. 17 is a diagram showing an SEM image of the substrate surface after electrodeposition in the comparative example.
  • FIG. 18 is a diagram showing a partially enlarged SEM image of FIG. BEST MODE FOR CARRYING OUT THE INVENTION
  • the method for producing a nanocarbon material according to the present invention includes the steps of: using a semiconductor on which a catalyst metal is formed non-uniformly as a cathode, and performing electrolysis in an electrolytic solution containing an organic solvent, so that the nanocarbon material Is formed.
  • the nanocarbon material produced according to the present invention refers to a carbon material having a structure having a size of about 0.111111 to several 10011 m.
  • Examples include tubular fibrous materials having a diameter of 0.111111 to several 10 nm), carbon nanowires (examples include solid fibrous materials having a diameter of several 100 nm), and carbon onions.
  • Examples are spherical fine particles having a diameter of several nm to several hundred nm and a graphite layer of several hundred to several hundred layers stacked in an onion shape), a radial aggregate of carbon nanowires (a large number of carbon nanowires are bundled radially). And expanded like a flower).
  • the present invention is suitable for producing an elongated fibrous material such as carbon nanotubes and carbon nanowires.
  • silicon is easily available and preferable, but other than this, a semiconductor such as germanium or a metal having a high resistance can be used. In the case where silicon is used, it is preferable to use silicon doped with impurities, since the electric resistance is reduced.
  • the catalyst metal is formed non-uniformly on the surface of the semiconductor.
  • the non-uniform formation referred to here is, for example, an island-like or granular dispersion formed on the semiconductor surface. It is thought that the current is concentrated on the portion where the catalyst metal is formed because the conductivity is higher than that of the semiconductor, and the carbon atoms of the organic solvent in the electrolyte are electrodeposited with the portion forming the nucleus as a nucleus.
  • the catalyst metal may be any as long as it has conductivity, and examples thereof include Ni, Co, Fe, Al, Cu, and Zn.
  • Ni, Co, and Fe are preferable, and particularly, Ni is most preferable, and then, Co and Fe are more preferable.
  • the catalyst metal is preferably formed on the surface of the semiconductor with a thickness of several nm to several 10 nm, preferably about 10 nm. Note that a plurality of types of catalytic metals (for example, Ni and Fe) and alloys thereof may be formed on one semiconductor.
  • each island-shaped (or granular) catalyst metal unevenly formed on the semiconductor surface is considered to determine the type of nanocarbon material mainly formed on the surface.
  • the size (diameter) of each catalyst metal is 0.1 to several 10 nm, preferably 0.1 nm.
  • 10 nm more preferably 0.1 to 0.5 nm, mainly a carbon nanotube is manufactured. This is because the electrolytic effect concentrates on the edge of the catalyst metal due to the so-called edge effect, and carbon is deposited on the edge, while electrodeposition becomes difficult at the center of the catalyst metal, and a tubular carbon nanotube grows. It is possible to do.
  • each catalyst metal when the size (diameter) of each catalyst metal is several 100 nm, preferably 100 to 200 ⁇ m, mainly carbon nanowires are produced.
  • the edge effect does not occur because the diameter increases, and an electrolytic current flows over the entire surface of the catalyst metal, carbon is deposited on the entire surface of the catalyst metal, and solid carbon-carbon nanowires grow. It is possible.
  • catalyst metals of various sizes (diameters) exist on the semiconductor surface various nanocarbon materials are formed according to the diameters.
  • Examples of a method for forming the catalyst metal non-uniformly on the semiconductor surface include, for example, a method in which electrolysis is performed using the semiconductor as a cathode in an electrolytic solution containing ions of the catalyst metal, and the catalyst metal is non-uniformly deposited on the surface of the semiconductor.
  • the catalyst metal can be formed non-uniformly by lowering the concentration of the catalyst metal ion in the electrolytic solution or by electrolyzing at a low current density.
  • the metal ions may be dissolved in the electrolyte in such an amount that the film thickness becomes about 10 nm. .
  • the concentration varies depending on the amount of the electrolytic solution. Therefore, the concentration is appropriately adjusted to meet the above conditions.
  • the electrolytic solution for example, a solution obtained by dissolving the above-mentioned catalyst metal nitrate (nickel nitrate, cobalt nitrate, ferrous nitrate, etc.) in an alcohol (eg, ethyl alcohol) can be used.
  • a method of forming the catalyst metal on the surface of the semiconductor and etching the catalyst metal there is a method of forming the catalyst metal on the surface of the semiconductor and etching the catalyst metal.
  • a catalytic metal such as Ni is formed on the surface of the semiconductor by sputtering to a predetermined thickness, and this is placed in an etching gas (for example, ammonia gas), whereby Ni is partially etched away.
  • the amount of metal ions in the electrolytic solution is increased so that the catalyst metal becomes large particles. can do.
  • the catalyst metal is usually The size of the grains is fairly widespread, with the size of large grains often a few meters and the size of small grains often a few nanometers.
  • the organic solvent contained in the electrolyte is not particularly limited, and examples thereof include alcohol, nitrile, benzene, and xylene.
  • alcohol such as methanol or ethanol, or tolethane-tolyl (acetonitrile) in methane is used.
  • Aliphatic nitriles are preferred.
  • the electrolyte may be an organic solvent alone, a mixture of a plurality of types of organic solvents, or a mixture of an organic solvent with water, a conduction aid, or the like.
  • the electrolytic solution is electrolyzed, and the anode is not particularly limited.
  • a carbon electrode, various insoluble anodes and the like can be used.
  • electrolytic conditions is not particularly limited, for example, to several 1 O m AZ cm 2, preferably may be direct electrolysis at a current density of 2 ⁇ 6 m AZ cm 2.
  • the electrolysis voltage (the voltage between the cathode and the anode) varies depending on the distance between the electrodes and the electric conductivity of the electrolyte, but is preferably 0.1 to a few tens of yen, more preferably 0.1 to 1 5 kV.
  • alternating electrolysis may be performed.
  • the above semiconductor may be used for either or both of the cathode and the anode.
  • the electrolysis temperature is not particularly limited, and may be a temperature at which the electrolyte does not boil, for example, room temperature to about 50 ° C.
  • the electrolytic solution may be appropriately cooled.
  • the electrolysis time varies depending on the electrolysis conditions. For example, the electrolysis may be performed for about 1 to 10 hours. .
  • an electrolytic device shown in FIG. 1 can be used.
  • an electrolyzer 10 includes an electrolyzer 2, a magnetic stirrer 3, a cathode 4 made of a semiconductor substrate, an anode 6, a thermometer 7, and a DC power supply 8.
  • the electrolytic bath 2 contains an electrolytic solution containing an organic solvent.
  • the catalyst metal 4 a is formed non-uniformly on the surface of the cathode 4 facing the anode 6. Then, by electrolysis, carbon atoms in the organic solvent are electrodeposited on the catalytic metal 4a and grow toward the anode 6 side.
  • the nanocarbon material prayed may be recovered by, for example, peeling it off from the catalytic metal by a mechanical method.
  • a nanocarbon material containing a catalyst metal or a nanocarbon material having a catalyst metal formed at the bottom can be obtained.
  • electrodeposition on semiconductors It may be used as it is.
  • FIG. 2 schematically show how the nanocarbon material is electrodeposited.
  • the catalytic metal 40a is formed in an island shape on the surface of the semiconductor substrate 40, and the nano-car is formed from the edge of the catalytic metal 40a toward the anode side (upward in the figure) by the edge effect described above.
  • the carbon material has grown and tubular carbon nanotubes have been formed.
  • the catalyst metal 41a is formed in an island shape on the surface of the semiconductor substrate 41, and in this case, the nanocarbon material is applied to the entire surface (including the side surface) of the catalyst metal 40a.
  • the catalyst has formed a carbon onion containing the catalyst metal.
  • the method for manufacturing a wiring structure of the present invention is performed in the same procedure as the above-described method for manufacturing a nanocarbon material, except that catalyst metals formed in a protruding shape at both ends of a wiring forming position are used as a cathode and an anode. It is different from the above method.
  • a nanocarbon material is formed as a wiring between a catalyst metal serving as a cathode and an anode. This will be described with reference to FIG.
  • wiring patterns 200 and 201 are formed on the surfaces of two circuit boards 100 and 101, respectively (FIG. 4 (a)). Now, it is assumed that the end (right end) of the wiring pattern 200 and the end (left end) of the wiring pattern 201 are to be wired and connected. In this case, first, the ends (right end) of the wiring pattern 200 and the ends (left end) of the wiring pattern 201, which are both ends of the wiring forming position, are formed with protrusions 200a made of a catalyst metal, respectively. 21a is formed in advance. Next, the wiring forming position including at least the protrusions 200a and 201a is immersed (or contacted) in an electrolytic solution containing an organic solvent. In this case, the entire circuit board 100, 101 may be immersed in the electrolytic solution, or an electrolytic cell in which only the wiring formation position is immersed in the electrolytic solution may be used.
  • the projections 200 a and 201 a are respectively used as a cathode and an anode (any one of them may be a cathode, but in this embodiment, the projection 200 a is assumed to be a cathode).
  • the nanocarbon material deposited on the protrusion 200a grows toward the protrusion 201a, and then the nanocarbon material is connected to the protrusion 201a. In this way, the nanocarbon material is formed as wiring 300 between the protrusions 200a and 201a. (Fig. 4 (b)).
  • the electrolysis may be DC electrolysis or alternating electrolysis.
  • the power source is connected to each wiring pattern 200, It may be connected to 201 and electrolyzed.
  • the size (diameter) of the protrusions 200a and 20la may be the same as the size (diameter) of the catalyst metal in the above-described method for producing a nanocarbon material, and by controlling the diameter, the nanocarbon material is obtained. This is also the same as in the case of the above-described method for producing a nanocarbon material.
  • the height of the protrusions 200a and 20la may be, for example, several nm to several 10 nm. The point is that the current only needs to be concentrated on the protrusions 200a and 201a.
  • a projection 2110a is formed in the wiring pattern 210, and a projection 2111a is formed in the wiring pattern 211.
  • the wiring patterns 210 and 211 are to be opposed to each other, and that wiring is to be performed between the protrusion 210a and the protrusion 211a.
  • the wiring pattern 210 is located above the wiring pattern 211, and the protrusion 210a is on an extension of the protrusion 211a.
  • the nanocarbon material is formed as the wiring 301 between the protrusions 210a and the protrusions 211a. It should be noted that even if the protrusion 2110a is shifted from the extension of the protrusion 211a to some extent, the nanocarbon material is formed as a wiring.
  • wiring can be performed at a low temperature such as room temperature using a nanocarbon material, and fine wiring, which has been extremely difficult in the past, can be easily performed. it can. That is, since current concentrates on the protruding portion at the wiring formation position, a nanocarbon material can be selectively deposited on a portion where wiring is desired to be formed as a wiring.
  • FIG. 1 shows an SEM (scanning electron microscope) image of a semiconductor substrate with non-uniform Ni.
  • the white part in the figure is the granular Ni, and the granular Ni with a size (diameter) of about 0.1 to 0.5 ⁇ is mainly seen.
  • Granular Ni with a nm particle size was also confirmed (not shown).
  • the semiconductor substrate produced by this etching method is referred to as substrate 1.
  • the electrolytic device shown in FIG. 1 was prepared.
  • the substrate 1 was used as a cathode.
  • a carbon rod with an outer diameter of 5 mm was used for the anode.
  • Electrolysis was performed using 5 OmL of methane nitrile (purity 99.5 vol%, reagent grade) as the electrolyte, current density 4 mA / cm 2 , distance between electrodes 5 mm, electrolysis voltage lkV, and electrolyte volume 50 mL. An electrodeposit was obtained on the cathode surface. Electrolysis was performed at room temperature, but the liquid temperature increased only 2-3 ° C after electrolysis. ⁇ Example 2>
  • non-uniform precipitation of Ni on the semiconductor substrate and electrodeposition of a nanocarbon material were simultaneously performed using the following electrolytic solution.
  • Electrolysis was carried out in exactly the same manner as in Example 1 above, except that the above-mentioned semiconductor substrate was used without forming Ni, and ethanol was used as the electrolytic solution. An electrodeposit was obtained.
  • the electrodeposits obtained in each Example and Comparative Example were identified by the following method.
  • SEM scanning electron microscope: JSM-5600 (electron beam: 15 kV)
  • TEM transmission electron microscope: JEOL
  • EDS Energy dispersive spectroscopy: an energy dispersive X-ray spectrometer, Link ISIS made by Oxford (electron beam 15 kV)
  • FIGS. 7 to 18 and Table 1 The results are summarized in FIGS. 7 to 18 and Table 1.
  • FIG. 7 is an SEM image of the substrate surface after electrodeposition in Example 2
  • FIG. 8 is a partially enlarged SEM image of FIG. 7
  • FIG. 9 is a partially enlarged SEM image of FIG.
  • FIG. 10 is a partially enlarged SEM image of FIG.
  • the white part indicates the precipitate
  • the black part indicates the deposit of the amorphous carbon film. It can be seen that this precipitate grows in a spike (needle) shape with a predetermined portion of the semiconductor substrate as a nucleus.
  • FIG. 11 is an SEM image of another place on the substrate surface after electrodeposition in Example 2
  • FIG. 12 is a partially enlarged SEM image of FIG.
  • the white portion indicates a precipitate, which indicates that the precipitate has grown into a fibrous form.
  • elemental analysis was performed by EDX on the same measurement area as the measurement samples in Figs. 7 and 11 above, and it was found that the white part in each figure was carbon. From FIGS. 7 to 12 described above, it can be seen that in Example 2, a fibrous carbon structure having a diameter of about 100 nm was generated, which can be said to be a carbon nanowire.
  • FIG. 13 is a TEM image of the electrodeposit in Example 2.
  • an onion-like carbon structure having a diameter of about 10 to 20 nm and a large number of graphite layers laminated is generated.
  • the composition of this structure is carbon from the result of the EDX analysis, and from these, the precipitate can be identified as carbon onion.
  • FIG. 14 shows the T values of the deposits in Example 2 in a different measurement area from Fig. 13.
  • FIG. 15 is a partially enlarged TEM image of FIG. According to FIG. 15, it can be seen that this fibrous precipitate has a large number of graphite layers laminated and a hollow core. According to Fig. 15, it can be read that the interval between the graphite layers is about 0.33 to 0.36 nm, and the outer diameter is about 30 nm and the inner diameter is about 2 nm. Usually, the layer spacing of carbon nanotubes is said to be 0.34 nm, from which the precipitate can be identified as carbon nanotubes.
  • FIG. 16 is an SEM image of the substrate surface after electrodeposition in Example 1, and a spiked electrodeposit with Ni as a nucleus can be seen in the center part of the figure, slightly to the right. According to EDX, this deposit was also composed of carbon, so it is considered to be a carbon nanowire.
  • FIG. 17 is an SEM image of the substrate surface after electrodeposition in the comparative example. Both the white and black parts in the figure are amorphous carbon films, and it is probable that the white and black parts were photographed due to differences in film thickness (irregularities on the film surface).
  • FIG. 18 is a partially enlarged SEM image of FIG. Although film-like substances were deposited on almost the entire surface of the substrate, no fibrous carbon materials such as carbon nanotubes and carbon nanowires were found. When Raman spectroscopy was performed on this film-like material, no sharp signal as seen in diamond-like force was observed. This is considered to be an amorphous carbon film.

Abstract

En effectuant l'électrolyse dans une solution électrolytique contenant un solvant organique au moyen d'un semi-conducteur sur lequel un métal catalyseur est formée de manière non uniforme sous forme d'une cathode, on forme un matériau de nanocarbone sur la surface du métal catalyseur.
PCT/JP2003/016831 2003-07-02 2003-12-25 Procede de production d'un materiau de nanocarbone et procede de fabrication d'une structure filaire WO2005003409A1 (fr)

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US10/563,018 US20060163077A1 (en) 2003-07-02 2003-12-25 Method for producing nanocarbon material and method for manufacturing wiring structure
CA002530976A CA2530976A1 (fr) 2003-07-02 2003-12-25 Procede de production d'un materiau de nanocarbone et procede de fabrication d'une structure filaire

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JP2003270361A JP4133655B2 (ja) 2003-07-02 2003-07-02 ナノカーボン材料の製造方法、及び配線構造の製造方法
JP2003-270361 2003-07-02

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TWI363367B (en) * 2007-12-26 2012-05-01 Tatung Co Composite field emission source and method of fabricating the same
WO2011111791A1 (fr) * 2010-03-11 2011-09-15 国立大学法人北海道大学 Procédé pour la production de nanotubes de carbone
US9075148B2 (en) * 2011-03-22 2015-07-07 Savannah River Nuclear Solutions, Llc Nano structural anodes for radiation detectors
CN104591855B (zh) * 2013-10-31 2017-07-25 刘广安 制备用于肥料的纳米碳粉的方法

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YOKOMICHI, H. "Ekisochu ni okeru Shitsuon deno Nano Carbon no Gosei", 2003 Nen Shunki Dai 50 Kai Oyo Butsurigaku Kankei Rengo Koenkai Koen Yokoshu, 27 March 2003, No. 2, page 1030 *
YOKOMICHI, H. "Electrochemical Deposition of Nanosize-Carbons, Dai 24 Kai Fullerene.Nanotube Sogo Symposium Koen Yoshishu, 08 January 2003, page 36 *

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