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WO2007108132A1 - Procede de production de nanotubes de carbone - Google Patents

Procede de production de nanotubes de carbone Download PDF

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Publication number
WO2007108132A1
WO2007108132A1 PCT/JP2006/305866 JP2006305866W WO2007108132A1 WO 2007108132 A1 WO2007108132 A1 WO 2007108132A1 JP 2006305866 W JP2006305866 W JP 2006305866W WO 2007108132 A1 WO2007108132 A1 WO 2007108132A1
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WO
WIPO (PCT)
Prior art keywords
substrate
fine particles
catalyst material
protrusions
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/305866
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English (en)
Japanese (ja)
Inventor
Akio Kawabata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujitsu Ltd
Original Assignee
Fujitsu Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujitsu Ltd filed Critical Fujitsu Ltd
Priority to JP2008506134A priority Critical patent/JP4850900B2/ja
Priority to PCT/JP2006/305866 priority patent/WO2007108132A1/fr
Publication of WO2007108132A1 publication Critical patent/WO2007108132A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Definitions

  • the present invention relates to a method for producing carbon nanotubes, and more particularly to a method for producing carbon nanotubes that can be produced by crosslinking isolated carbon nanotubes.
  • Carbon nanotubes basically have a structure in which a dalaphen sheet with a hexagonal network structure of carbon atoms is rolled into a cylindrical shape.
  • SWNT single-walled nanotubes
  • DWNT double-walled single-bonn nanotubes
  • Carbon nanotubes with electrical or semiconducting electrical properties and semiconducting electrical properties can be expected to be applied to electronic devices.
  • Patent Document 1 proposes a structure of an electrode that is electrically connected to a multi-walled carbon nanotube. According to this, the carbon nanotube is cut immediately before forming the electrode, and a metal that forms a strong and ionic bond with the carbon atom is formed on the cut carbon nanotube to form the electrode. As a result, the contact resistance between the electrode and the carbon nanotube is reduced, and it is attempted to be applied to electronic devices!
  • Patent Document 2 proposes a field effect transistor in which a metallic inner layer of a double-walled carbon nanotube is used as a gate electrode and a semiconducting outer layer is used as a channel. Patent Document 2 also discloses a field effect transistor in which a semiconducting inner layer of two-walled carbon nanotubes is used as a channel region and a metallic outer layer is used as a gate electrode as a prior art.
  • carbon nanotubes need to be generated in a state of being isolated and hanging in a hollow state without contacting the substrate. If the carbon nanotubes are in contact with the substrate, the characteristic evaluation signal will be weak, and if multiple carbon nanotubes are bundled (bundled), fluorescence will not be seen. This is because evaluation becomes difficult. Therefore, the present condition is to select the carbon nanotubes that are in a state of floating in the air alone from the many grown carbon nanotubes, and to characterize them. However, if the force grows in a bundled state, it becomes difficult to take out single bonn nanotubes with the desired characteristics and support them on the substrate.
  • Patent Document 3 fine protrusions are formed on the surface of a silicon substrate, a portion other than the protrusion tips is coated with a photosensitive resist, a catalyst metal is applied only to the protrusion tips, and a desired metal is applied to the catalyst metal by CVD.
  • the production of carbon nanotubes of diameter is described. According to this method, it is expected to generate carbon nanotubes with the tip force of the protrusions, and it is expected to reproduce the state of being hung alone.
  • Patent Literature l WO 02 / 063693A1
  • Patent Document 2 JP 2004-171903 A
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-182537
  • Patent Document 3 The generation method of Patent Document 3 described above requires a process of forming protrusions on the surface of the silicon substrate, and covering with a photosensitive resist leaving the tip. However, in this process, it is necessary to control the height of the protrusion and the film thickness of the photosensitive resist with high precision, which is not a realistic generation method. Depending on the size of the catalyst metal formed at the tip of the protrusion, the growth Although the diameter and the number of layers of the carbon nanotubes can be controlled, it is difficult to control the size of the catalyst metal with good reproducibility for the same reason as above.
  • an object of the present invention is to provide a carbon nanotube production method capable of producing a large amount of hollow carbon nanotubes with good reproducibility.
  • a first step of preparing a first substrate having a plurality of protrusions formed on the surface, and a second substrate A second step of generating a plurality of fine particles comprising a catalyst material, and contacting a plurality of protrusions formed on the first substrate with the fine particles of the catalyst material formed on the second substrate, A third step of attaching the fine particles of the catalyst material to the plurality of protrusions, and a fourth step of growing the carbon nanotubes on the fine particles of the catalyst material by placing the first substrate in a carbon-containing gas atmosphere. It is the production method of the carbon nanotube which has.
  • the catalyst material is a transition metal containing at least cobalt, iron, and nickel.
  • the catalyst material is an alloy of a transition metal containing at least cobalt, iron, or nickel and a metal of Ti, Al, Ta, TiN, or Ti02.
  • the protrusion of the first substrate is in contact with the fine particles of the catalyst material of the second substrate. , Heat to a predetermined temperature to attach fine particles of catalyst material to the protrusions.
  • Ti, Al are formed on the plurality of protrusion surfaces of the first substrate prepared in the first step.
  • the transition material fine particles are transition metal fine particles having a diameter of 0.5 to LOnm, and the carbon nanotubes grown in the fourth step are 1 to 4nm in diameter. Single or double layered in diameter.
  • a first step of preparing a first substrate having a plurality of protrusions formed on the surface, and a step on the second substrate Made of catalyst material A second step of generating a plurality of fine particles; and a plurality of protrusions formed on the first substrate are brought into contact with the fine particles of the catalyst material formed on the second substrate;
  • a method for producing a fine wire substance comprising: a third step of attaching fine particles of material; and a fourth step of placing the first substrate in a growth gas atmosphere to grow fine wire substance on the fine particles of the catalyst material. is there.
  • the catalyst material is Au
  • the fine wire substance is a group IIIV compound semiconductor containing GaAs, InP, InAs, and a fourth process force.
  • This is a metalorganic chemical vapor deposition method using III group V metal gas as the growth gas.
  • a first step of generating a plurality of fine particles of a catalyst material on a substrate Etching with the fine particles as a mask to form a plurality of protrusions having the fine particles attached to the tips, and placing the substrate in a growth gas atmosphere to grow fine wire substances on the fine particles of the catalyst material
  • a third step of producing a fine wire substance a first step of generating a plurality of fine particles of a catalyst material on a substrate, Etching with the fine particles as a mask to form a plurality of protrusions having the fine particles attached to the tips, and placing the substrate in a growth gas atmosphere to grow fine wire substances on the fine particles of the catalyst material.
  • FIG. 1 is a cross-sectional view showing a carbon nanotube production process according to the first embodiment.
  • FIG. 2 is a cross-sectional view showing a carbon nanotube production process according to the first embodiment. It is a figure explaining the laser abrasion method.
  • FIG. 4 is a cross-sectional view showing a production process of carbon nanotubes according to the first embodiment
  • FIG. 5 is a sectional view showing a carbon nanotube production step according to the first embodiment.
  • FIG. 6 is a cross-sectional view showing a carbon nanotube production step according to the first embodiment.
  • FIG. 7 is a schematic configuration diagram of a CVD apparatus.
  • FIG. 8 is a view showing a carbon nanotube CNT generated by the third embodiment.
  • FIG. 9 is a cross-sectional view showing a production process of the fifth embodiment.
  • FIGS. 1, 2, 4, 4, and 6 are cross-sectional views showing the carbon nanotube production process according to the first embodiment.
  • a substrate having a plurality of fine needle-like protrusions 12 formed on the surface for example, a silicon substrate 10 is prepared.
  • the fine protrusions 12 are formed, for example, by forming a resist layer having a predetermined pattern on the surface of the silicon substrate 10 and etching the substrate surface using the mask as a mask to form irregularities having a rectangular cross section. This can be achieved by processing the concavo-convex protrusion into a protrusion 12 with a sharp tip by a wet etching method having anisotropy in a predetermined crystal direction.
  • fine particles 22 of catalyst material are supported on the surface of a substrate 20 such as silicon.
  • This catalyst material is a transition metal containing, for example, nickel, iron, and cobalt when growing carbon nanotubes. Or transition metal and Ti,
  • the diameter of the fine particles is controlled to about 0.5 to: LOnm, preferably about 1 to 4 nm.
  • Fine particles whose diameter is controlled to about LOnm are generated on the substrate surface by the laser ablation method developed by the present inventors.
  • the method of producing these fine particles is It is introduced in detail in Chemical Physics Letters 382 (2003) 361.
  • FIG. 3 is a diagram for explaining the laser ablation method. The method is briefly described below.
  • an iron target 32 is set in a chamber 30 containing He gas and having a pressure of 1.5 KPa, and the target is irradiated with a laser beam 36 from an Nd, YAG laser 34 to ablate the iron target 32 ( Excise).
  • the iron of the target 32 evaporates by irradiation with a single laser beam 36 having energy, and immediately after that, solidifies to produce fine particles 40. These fine particles are annealed when passing through the vicinity of the tube-shaped heating means 42 by the He gas flow, and the crystal state thereof is improved.
  • the particle size of the iron fine particles 40 to be generated has a certain variation, the particle size is 0.5 to: LOnm, preferably 1.0 to 4 by DM A (Differential Mobility Analyzer) 44.
  • Fine particles having a particle size of Onm are selected, introduced into the chamber 46, and supported on the surface of the second substrate 20 as fine particles 22 of the catalyst material.
  • a voltage is applied to the stage 28 of the substrate 20, and the charged fine particles 22 fall on the surface of the substrate 20 due to a potential difference.
  • the first substrate 10 having a plurality of protrusions formed on the surface is turned upside down so as to face the second substrate 20 carrying a large number of fine particles 22 of catalyst material. Then, the tip of the protrusion 12 is brought into contact with the fine particle 22 to attach the fine particle 22 to the tip of the protrusion. As a result, as shown in FIG. 5, one particle 22 is attached to the tip of the protrusion 12 of the first substrate 10.
  • the fine particles can be more efficiently attached to the tips of the protrusions by heating to, for example, about 300 ° C. while the tips of the protrusions 12 are in contact with the fine particles 22.
  • This heating temperature is considerably lower than the melting point of catalytic metals such as iron, but the metal is easily attached by heating.
  • the fine particles 22 are supported on the surface of the substrate 20 without gaps. However, if there are gaps between the fine particles 22 to some extent, the projection 12 is more effective in the adhesion process of FIG.
  • One fine particle 22 can be separated and attached to the tip of the substrate. As described above, the particle size of the catalyst metal fine particles 22 is adjusted to a desired value, and by using the catalyst metal fine particles 22 having such a controlled particle size, carbon nanotubes having a uniform diameter are grown. To let it can. Therefore, it is desirable to attach a single particle 22 to the tip of each protrusion.
  • the first substrate is introduced into the chamber of the thermal CVD apparatus, and while the substrate is heated to about 600 ° C., argon (Ar), acetylene (C2H2), hydrogen Carbon nanotubes CNT are grown on the catalytic metal fine particles 22 in an atmosphere of 0.1 to lKPa in a mixed gas of (H2) (ratio 90: 10: 1000). Carbon nanotubes CNT start growing at a diameter corresponding to the particle size of the fine particles 22, and the tip reaches the surface of the adjacent protrusion.
  • Ar argon
  • C2H2 acetylene
  • the length of the carbon nanotube CNT can be controlled, and the carbon nanotube isolated in the hollow from the catalytic metal fine particle 22 to the adjacent protrusion 22 CNT can be grown.
  • FIG. 7 is a schematic configuration diagram of the above CVD apparatus.
  • a stage 52 and a heating means 54 made of hot filament are provided in a chamber 50.
  • a voltage 56 is applied to the hot filament 54 to generate heat, and the surface of the first substrate placed on the stage 52 is heated.
  • a mixed gas of argon (Ar), acetylene (C2H2), and hydrogen (H2) (ratio 90: 10: 1000) 58 is introduced into the chamber 50 as the growth gas. maintained at lKPa.
  • Ar argon
  • C2H2H2H2 acetylene
  • H2H2H2 hydrogen
  • the surface of the first substrate 10 is heated to about 600 ° C.
  • carbon nanotube CNTs grow from the catalytic metal particles 22.
  • the present inventors by adjusting the diameter of the iron fine particles 22 to about 0.5 to 4 nm, it was possible to grow one or two-layer carbon nanotubes with a diameter of about 1 to 4 nm. Therefore, by attaching a single iron fine particle 22 to the tip 12, carbon nanotubes having a uniform diameter and a uniform number of layers can be generated in isolation.
  • transition metals such as iron, cobalt, and nickel were used as catalyst materials.
  • a mixture of these catalyst metals and any one of Ti, Al, Ta, TIN, and Ti02 is used. Therefore, the target 32 shown in Fig. 3 is replaced with the above mixed metal material.
  • the mixed metal fine particles 22 can be supported on the surface of the second substrate 20 by the same manufacturing method.
  • Other processes are the same as those in the first implementation. The form is the same.
  • fine particles mixed with both metals are generated by laser ablation using a mixed substrate of 80% coronate and 20% titanium as the target 32.
  • a metal film of Ti, Al, Ta, TiN, or Ti02 is deposited on the surface of the needle-like protrusion 12 of the first substrate 10 shown in FIG. It is formed to a film thickness of about.
  • catalytic metal fine particles 22 such as cobalt are attached to the protrusions 12 according to the procedures shown in FIGS. 2, 4, and 5, and carbon nanotubes are grown by thermal CVD or hot filament CVD.
  • FIG. 8 is a diagram showing the carbon nanotube CNT generated by the third embodiment.
  • a titanium film 12 is formed on the surface of the needle-like protrusion 12, and carbon nanotubes CNT grow on cobalt fine particles 22 attached on the titanium film 12.
  • the substrate is heated to, for example, 650 ° C, a mixed gas of alcohol and hydrogen such as argon and ethanol is introduced, maintained at a pressure of 0.1 KPa, and held for about 40 minutes.
  • the growing carbon nanotube CNT forms an ohmic contact with low resistance between the titanium film 12.
  • the tip of the growing carbon nanotube CNT also forms a low-resistance ohmic contact with the titanium film.
  • the cobalt fine particles may be fine particles of other transition metals, fine particles of a mixture of transition metal and Ti, Al, Ta, TiN, Ti02 (V, any metal!
  • the carbon nanotube generation method has been described.
  • it is a method for producing a thin wire material that is not a carbon nanotube but a IIIV compound semiconductor.
  • a first substrate 10 having needle-like protrusions 12 is prepared.
  • the second A catalyst metal for example, gold fine particles 22 is supported on the surface of the substrate 20. 4 and 5, gold fine particles 22 are attached to the tips of the protrusions 12 of the first substrate 10.
  • the first substrate is loaded into the MOCVD (Metal Organic Chemical Vapor Deposition) equipment, and the fine wire material, III-V compound semiconductor, is grown on the catalyst particles 22 in the III-V metal gas atmosphere. Let Similar to the carbon nanotube CNT shown in Fig. 6, this fine wire material grows from catalyst fine particles 22 and becomes a thin rod-like material that reaches the surface of the adjacent protrusion 12.
  • MOCVD Metal Organic Chemical Vapor Deposition
  • FIG. 9 is a cross-sectional view showing the generation process of the fifth embodiment.
  • step (a) fine particles 22 of the catalyst material are generated on the surface of the first substrate 10 by the method described above.
  • step (b) using the fine particles 22 as a mask, the surface of the first substrate 10 is etched by, for example, ion milling to form needle-like protrusions 12.
  • step (b) using the fine particles 22 as a mask, the surface of the first substrate 10 is etched by, for example, ion milling to form needle-like protrusions 12.
  • this is the same state as in Fig. 5.
  • the growth gas for chemical vapor deposition in the first to fifth embodiments described above may be a gas obtained by vaporizing a carbon-containing liquid in addition to acetylene and alcohol.
  • nitrogen may also be used.
  • N2 may be used, and in addition to argon Ar, helium He may be used.
  • a gas obtained by vaporizing a carbon-containing liquid such as hydrocarbon or alcohol may be used alone, or a mixed gas mixed with at least one of hydrogen, nitrogen, argon, and helium may be used. You can use it.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de production de nanotubes de carbone, comprenant le fait de proposer un premier substrat (10) possédant une multitude de projections sur sa surface ; la formation d'une multitude de microparticules d'un matériau de catalyseur sur un second substrat ; le fait de mettre en contact la multitude de projections (12) sur le premier substrat avec la multitude de microparticules de matériau de catalyseur sur le second substrat de façon à adhérer de ce fait les microparticules de matériau de catalyseur sur la multitude de projections ; et le fait de placer le premier substrat sous une atmosphère de gaz carbonique de façon à développer de ce fait des nanotubes de carbone sur les microparticules de matériau de catalyseur. On forme ainsi des nanotubes de carbone isolés entre les projections.
PCT/JP2006/305866 2006-03-23 2006-03-23 Procede de production de nanotubes de carbone Ceased WO2007108132A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2008506134A JP4850900B2 (ja) 2006-03-23 2006-03-23 カーボンナノチューブの生成方法
PCT/JP2006/305866 WO2007108132A1 (fr) 2006-03-23 2006-03-23 Procede de production de nanotubes de carbone

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Application Number Priority Date Filing Date Title
PCT/JP2006/305866 WO2007108132A1 (fr) 2006-03-23 2006-03-23 Procede de production de nanotubes de carbone

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WO2007108132A1 true WO2007108132A1 (fr) 2007-09-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173497A (ja) * 2008-01-25 2009-08-06 Mie Univ 準結晶触媒を用いるカーボンナノチューブ合成法

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JP2001020071A (ja) * 1999-06-11 2001-01-23 Cheol Jin Lee カーボンナノチューブの合成方法
JP2001081564A (ja) * 1999-07-27 2001-03-27 Cheol Jin Lee 化学気相蒸着装置およびこれを用いたカーボンナノチューブ合成方法
JP2004051432A (ja) * 2002-07-19 2004-02-19 Fujitsu Ltd カーボンナノチューブの製造用基板及びそれを用いたカーボンナノチューブの製造方法
JP2004182537A (ja) * 2002-12-04 2004-07-02 Mie Tlo Co Ltd ナノカーボン材料配列構造の形成方法
JP2004241295A (ja) * 2003-02-07 2004-08-26 Hitachi Zosen Corp カーボンナノチューブを用いた電子放出素子用電極材料およびその製造方法
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JP2001020071A (ja) * 1999-06-11 2001-01-23 Cheol Jin Lee カーボンナノチューブの合成方法
JP2001081564A (ja) * 1999-07-27 2001-03-27 Cheol Jin Lee 化学気相蒸着装置およびこれを用いたカーボンナノチューブ合成方法
JP2004051432A (ja) * 2002-07-19 2004-02-19 Fujitsu Ltd カーボンナノチューブの製造用基板及びそれを用いたカーボンナノチューブの製造方法
JP2004182537A (ja) * 2002-12-04 2004-07-02 Mie Tlo Co Ltd ナノカーボン材料配列構造の形成方法
JP2004241295A (ja) * 2003-02-07 2004-08-26 Hitachi Zosen Corp カーボンナノチューブを用いた電子放出素子用電極材料およびその製造方法
JP2005246507A (ja) * 2004-03-02 2005-09-15 Pioneer Electronic Corp 先端部への物質配置装置
JP2005272171A (ja) * 2004-03-23 2005-10-06 Nippon Telegr & Teleph Corp <Ntt> カーボンナノチューブの製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173497A (ja) * 2008-01-25 2009-08-06 Mie Univ 準結晶触媒を用いるカーボンナノチューブ合成法

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