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WO2016158286A1 - Matériau de base permettant la production de nanotubes de carbone et procédé de production de nanotubes de carbone - Google Patents

Matériau de base permettant la production de nanotubes de carbone et procédé de production de nanotubes de carbone Download PDF

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Publication number
WO2016158286A1
WO2016158286A1 PCT/JP2016/057554 JP2016057554W WO2016158286A1 WO 2016158286 A1 WO2016158286 A1 WO 2016158286A1 JP 2016057554 W JP2016057554 W JP 2016057554W WO 2016158286 A1 WO2016158286 A1 WO 2016158286A1
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WIPO (PCT)
Prior art keywords
base material
film layer
crystallized glass
carbon nanotube
glass substrate
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Ceased
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PCT/JP2016/057554
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English (en)
Japanese (ja)
Inventor
武史 土谷
佐々木　博
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Filing date
Publication date
Priority claimed from JP2015217263A external-priority patent/JP2016190780A/ja
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Publication of WO2016158286A1 publication Critical patent/WO2016158286A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01J23/745—Iron
    • 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
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • B01J35/36—Mechanical strength
    • 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material

Definitions

  • the present invention relates to a carbon nanotube production base material and a carbon nanotube production method, and more specifically, a carbon nanotube production base material used for production of carbon nanotubes using a chemical vapor deposition method (CVD method), and carbon nanotubes It relates to a manufacturing method.
  • CVD method chemical vapor deposition method
  • carbon nanotubes have attracted attention as an excellent structural material because they have a very stable structure chemically and mechanically and are lightweight. Moreover, the usefulness of carbon nanotubes has also been confirmed in applications such as semiconductors, electronic devices, optical devices, batteries, and the like due to their electrical characteristics.
  • Patent Document 1 discloses a method of manufacturing carbon nanotubes using a thermal CVD method. Specifically, a method of growing a carbon nanotube on a substrate by heating a growth base material on which a catalytic metal is deposited and decomposing a hydrocarbon gas on the substrate is disclosed.
  • Patent Document 1 In order to produce high-quality carbon nanotubes with good orientation using the technique disclosed in Patent Document 1, it is difficult for the substrate to be deformed in a processing temperature range (for example, 600 to 1100 ° C. in Patent Document 1). is important. For this reason, the substrate used in the method is limited to materials that are difficult to be deformed in a high-temperature atmosphere such as quartz, crystalline alumina, and crystalline silicon.
  • the present invention has been made in view of such circumstances, and it is an object of the present invention to provide a carbon nanotube production substrate and a carbon nanotube production method capable of producing carbon nanotubes at low cost and high efficiency. To do.
  • the base material for producing carbon nanotubes of the present invention is a base material for producing carbon nanotubes used as a base material for growing carbon nanotubes, and is characterized by comprising a catalytic metal thin film layer on the surface of a crystallized glass base material.
  • the crystallized glass base material contains an alkali metal oxide, and the elution prevention prevents the elution of alkali metal ions between the crystallized glass base material surface and the catalytic metal thin film layer. It is preferable to further comprise a membrane layer.
  • the elution preventing film layer includes at least one material selected from the group of SiO 2 , ZrO 2 , SnO 2 , TiO 2 , TiN, and Al 2 O 3. preferable.
  • the elution preventing film layer contains a crystalline metal oxide.
  • the elution preventing film layer has a composition containing 60 to 96% SiO 2 and 4 to 40% Al 2 O 3 by mass%.
  • the elution preventing film layer has a thickness of 50 to 800 nm
  • the crystallized glass base material has a plate shape whose main surface has a surface area of 15000 mm 2 or more.
  • the thickness of the crystallized glass substrate is preferably 0.2 to 5.0 mm.
  • the thermal expansion coefficient at 30 to 380 ° C. of the crystallized glass substrate is ⁇ 1 to 12 ⁇ 10 ⁇ 7 / ° C., and 30 to 750 ° C. of the crystallized glass substrate. It is preferable that the thermal expansion coefficient at ⁇ 1 to 15 ⁇ 10 ⁇ 7 / ° C.
  • the crystallized glass base material has a composition of mass%, SiO 2 55 to 75%, Al 2 O 3 20.5 to 27%, Li 2 O 2% or more, TiO 2 1.5 to 3%, TiO 2 + ZrO 2 3.8 to 5%, SnO 2 0.1 to 0.5%, V 2 O 5 0 to 1% are preferably contained.
  • the catalytic metal thin film layer preferably contains at least one metal selected from the group consisting of Fe, Co, Ni, Pt, Mo, and Pd.
  • the base material for producing carbon nanotubes of the present invention is a base material for producing carbon nanotubes used as a base material for growing carbon nanotubes, and elution of alkali metal ions on the surface of a crystallized glass base material containing an alkali metal oxide It is characterized in that an elution preventing film layer for preventing the above is provided.
  • the carbon nanotube production method of the present invention comprises a catalyst film forming step of forming a catalyst metal thin film layer on a crystallized glass substrate to obtain a growth substrate, and a growth substrate in a temperature atmosphere exceeding 600 ° C. And a growth step of growing a carbon nanotube by circulating a gas containing a carbon raw material.
  • the crystallized glass substrate includes an alkali metal oxide as a composition, and an elution preventing film forming step of forming an alkali metal oxide elution preventing film layer on the surface of the crystallized glass substrate It is preferable that a catalyst film formation step is performed after the elution film formation step.
  • the carbon nanotubes are reduced. It can be manufactured at low cost and high efficiency.
  • carbon nanotube is also referred to as “CNT”.
  • FIG. 1 is a diagram showing a configuration of a carbon nanotube production substrate 1 (hereinafter also referred to as a CNT production substrate 1) according to an embodiment of the present invention.
  • the substrate 1 for producing CNT includes a crystallized glass substrate 2 and a catalytic metal thin film layer 3.
  • the crystallized glass substrate 2 is, for example, a Li 2 O—Al 2 O 3 —SiO 2 based crystallized glass containing an alkali metal oxide. More specifically, the crystallized glass substrate 2 has a composition of mass%, SiO 2 55 to 75%, Al 2 O 3 20.5 to 27%, Li 2 O 2% or more, TiO 2 1.5 to 3%, TiO 2 + ZrO 2 3.8 to 5%, SnO 2 0.1 to 0.5%, V 2 O 5 0 to 1%, and glass substrate containing ⁇ -spodumene solid solution as the main crystal It is.
  • the crystallized glass substrate 2 preferably has a thermal expansion coefficient of ⁇ 1 to 12 ⁇ 10 ⁇ 7 / ° C. at 30 to 380 ° C. and a thermal expansion coefficient of ⁇ 1 to 15 ⁇ 10 ⁇ 7 at 30 to 750 ° C. More preferably, the temperature is / ° C. With such a thermal expansion coefficient, it is difficult to be deformed even in a high-temperature heat treatment during the CNT manufacturing process, so that CNTs with good orientation can be obtained.
  • the shape of the crystallized glass substrate 2 may be arbitrarily determined, for example, a rectangular, circular, or elliptical plate shape is preferable because it can be easily processed and handled.
  • the surface area of the main surface of the crystallized glass substrate 2 is preferably 15000 mm 2 or more, more preferably 80000 to 150,000 mm 2 . With such a surface area, CNTs can be produced more efficiently than conventional substrates.
  • the thickness of the crystallized glass substrate 2 is preferably 0.2 to 5.0 mm. When the thickness of the crystallized glass substrate 2 is smaller than 0.2 mm, the substrate 1 for CNT production becomes easily bent, and thus the handling in the CNT production process is deteriorated or the orientation of the CNT is lowered. There is. Also, if the thickness of the crystallized glass substrate 2 is greater than 5.0 mm, the amount of expansion (or shrinkage) of the substrate 1 for CNT production in the CNT production process increases, so the quality such as the orientation of CNTs. May decrease.
  • the catalytic metal thin film layer 3 is a catalyst layer that reacts with a hydrocarbon gas during the production of CNTs.
  • the catalytic metal thin film layer 3 is preferably a film layer made of one kind selected from the group consisting of Fe, Co, Ni, Pt, Mo, and Pd, or an alloy thereof.
  • the thickness of the catalytic metal thin film layer 3 is preferably about 5 to 80 nm, for example. If the thickness of the catalytic metal thin film layer 3 is smaller than 5 nm, the reaction with the hydrocarbon gas necessary for the growth of CNTs may not occur sufficiently, or the catalytic metal thin film layer 3 may be easily peeled off. If the thickness of the catalytic metal thin film layer 3 is greater than 80 nm, the film formation cost increases.
  • the base material 1 for CNT production may be configured to further include an elution preventing film layer 4 that prevents elution of alkali metal ions between the surface of the crystallized glass base material 2 and the catalytic metal thin film layer 3. With such a configuration, it is possible to prevent alkali metal ions from being eluted from the crystallized glass substrate 2 and inhibiting the growth of CNTs.
  • the elution preventing film layer 4 is preferably a film layer containing at least one material selected from the group of SiO 2 , ZrO 2 , SnO 2 , TiO 2 , TiN, and Al 2 O 3 , for example. More specifically, the elution prevention film layer 4 is particularly preferably a film layer containing, for example, crystalline ZrO 2 . According to such a film layer, it is possible to dramatically improve the elution prevention performance of alkali metal ions. Since ZrO 2 having crystallinity is denser than a film having an amorphous structure having an irregular arrangement, it is presumed that such an effect can be obtained.
  • the elution preventing film layer 4 is a film layer having a composition containing 60 to 96% SiO 2 and 4 to 40% Al 2 O 3 in terms of mass%.
  • Al 2 O 3 By adding an appropriate amount of Al 2 O 3 to the SiO 2 film layer, the elution prevention performance of alkali metal ions can be drastically improved, and the mechanical durability is higher than that of a film layer composed only of metal components such as Al 2 O 3. And chemical durability can be obtained.
  • the thickness of the elution preventing film layer 4 is preferably 50 to 800 nm, for example, and more preferably 80 to 250 nm.
  • composition and configuration of the elution preventing film layer 4 are merely examples, and any composition and configuration may be adopted as long as permeation of alkali metal ions can be suppressed. Further, when the crystallized glass substrate 2 does not contain an alkali metal oxide or when the elution amount of alkali metal ions from the crystallized glass substrate 2 is small, an elution preventing film layer is formed on the CNT manufacturing substrate 1. 4 may be provided.
  • a sputtering method is suitable as a method for forming the catalytic metal thin film layer 3 and the elution preventing film layer 4.
  • the catalyst metal thin film layer 3 and the elution preventing film layer 4 can be formed in a uniform and thin thickness.
  • the catalyst metal thin film layer 3 is formed into a film.
  • a catalytic metal thin film layer 3 is formed on a crystallized glass substrate 2 as described above to obtain a substrate 1 for producing CNTs.
  • a raw material gas containing a carbon raw material is circulated on the substrate for manufacturing CNTs 1 for a predetermined growth time in a temperature atmosphere exceeding 600 ° C. to grow CNTs on the substrate.
  • the source gas is, for example, a hydrocarbon gas.
  • the growth temperature of the CNT is preferably 750 to 1500 ° C, more preferably 800 to 1200 ° C, still more preferably 850 to 1100 ° C, and 900 to 1000 ° C. When the growth atmosphere temperature of CNT is 600 ° C.
  • the CNT growth time may be arbitrarily set according to the growth atmosphere temperature or the like, and is, for example, 5 to 40 minutes. If it is this time, even if it is a high temperature atmosphere of 800 degreeC or more, the base material 1 for CNT manufacture will hardly deform
  • the carbon nanotube production substrate 1 and the carbon nanotube production method using the same is inexpensive but has high heat resistance and easily has a large area. Since the carbon nanotube production substrate 1 is configured using the crystallized glass substrate 2 that can be formed into a plate shape, carbon nanotubes can be produced at low cost and high efficiency.
  • the shape of the crystallized glass substrate 2 is an example, and may be any shape such as a housing shape, a sheet shape, a pellet shape, or a wire shape.
  • the method for forming the catalytic metal thin film layer 3 and the elution preventing film layer 4 is not limited to the above method, and any film forming method may be used.
  • the catalytic metal thin film layer 3 and the elution preventing film layer 4 may be formed by vapor deposition.
  • Table 1 shows examples (Nos. 1 to 3) and comparative examples (No. 4) of the present invention.
  • a Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass substrate is used as the base material of the example, and a B 2 O 3 —SiO 2 -based amorphous glass base material is used as the base material of the comparative example.
  • a Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass substrate is used as the base material of the example, and a B 2 O 3 —SiO 2 -based amorphous glass base material is used as the base material of the comparative example.
  • the composition is SiO 2 65.6%, Al 2 O 3 22.2%, Li 2 O 3.7%, Na 2 O 0.4%, K 2 O 0.
  • the glass raw material is made to be a glass containing 3%, MgO 0.7%, BaO 1.2%, TiO 2 2%, ZrO 2 2.2%, P 2 O 5 1.4%, SnO 2 0.3%.
  • Preparation and melting were performed, and the obtained molten glass was formed into a plate shape using a roll-out method. Next, the obtained plate glass was heated to precipitate a ⁇ -spodumene solid solution as a main crystal, thereby obtaining a crystallized glass substrate.
  • an amorphous glass substrate When preparing an amorphous glass substrate, it becomes a glass containing SiO 2 81%, B 2 O 3 13%, K 2 O + Na 2 O 4%, Al 2 O 3 2% by mass% as a composition. A glass raw material was prepared and melted, and the resulting molten glass was formed into a plate shape by using a float process to obtain an amorphous glass substrate.
  • No. 1 shown in Table 1 was formed on the main surface of the crystallized glass substrate obtained as described above. 1 and no. Regarding the sample of 2, the elution prevention film layer was formed by forming the film material shown in the same table using the sputtering method. Further, the crystallinity of the obtained elution preventing film layer was measured by using an X-ray analyzer SmartLab manufactured by Rigaku Corporation. Specifically, a peak showing crystallinity was measured with the apparatus, and when the diffraction peak could be observed, the crystallinity was determined, and when the diffraction peak could not be observed, the crystallinity was determined not.
  • Fe was formed as a catalyst metal thin film layer on the surface of each glass substrate using a sputtering method, and each sample shown in Table 1 was obtained.
  • CNTs were produced using each sample obtained as described above as a substrate for producing carbon nanotubes, and the number density of the produced carbon nanotubes was evaluated.
  • the number density is the number per unit area of CNTs grown in a vertical alignment on the substrate surface.
  • the CNT grown by the above production method was excluded, and the substrate surface was observed with an electron micrograph. Since the substrate grown in the vertical orientation is densely grown, the number density increases, which becomes an index for evaluating quality and productivity.
  • Example 1 since a crystalline ZrO 2 film was used as the alkali elution preventing film, a number density of 5 ⁇ 10 9 / cm 2 was obtained. No. In Example 2, since it has a SiO 2 film having an amorphous structure, a number density of 3 ⁇ 10 9 / cm 2 was obtained. Due to the crystallinity, the alkali ion diffusibility is suppressed and the number density is considered to have grown.
  • the base material for carbon nanotube production and the carbon nanotube production method of the present invention are useful as a substrate and method for enabling efficient production of carbon nanotubes used in structural materials, semiconductors, electronic equipment, optical equipment, batteries, etc. is there.
  • Carbon nanotube production substrate (CNT production substrate) 2 Crystallized glass substrate 3 Catalyst metal thin film layer 4 Elution prevention film layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un matériau de base permettant la production de nanotubes de carbone conçu pour être utilisé comme matériau de base permettant la croissance de nanotubes de carbone, le matériau de base permettant la production de nanotubes de carbone étant caractérisé en ce qu'une couche catalytique de film fin métallique est prévue sur la surface d'un matériau de base en verre-céramique. Dans ce matériau de base permettant la production de nanotubes de carbone, le matériau de base en verre-céramique contient de préférence un oxyde de métal alcalin et est également prévu avec une couche formant film de prévention de l'élution pour prévenir l'élution d'ions métalliques alcalins entre la surface du matériau de base en verre-céramique et la couche catalytique de film fin métallique.
PCT/JP2016/057554 2015-03-30 2016-03-10 Matériau de base permettant la production de nanotubes de carbone et procédé de production de nanotubes de carbone Ceased WO2016158286A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015068166 2015-03-30
JP2015-068166 2015-03-30
JP2015-217263 2015-11-05
JP2015217263A JP2016190780A (ja) 2015-03-30 2015-11-05 カーボンナノチューブ製造用基材およびカーボンナノチューブ製造方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002542136A (ja) * 1999-04-16 2002-12-10 コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション 多層炭素ナノチューブフィルム
JP2003510462A (ja) * 1999-09-29 2003-03-18 エレクトロファク，ファブリカツィオーン エレクトロテクニシャー スペツィアラルティクテル ゲゼルシャフト ミット ベシュレンクテル ハフツング 基材上にナノチューブ層を生成する方法
JP2005272284A (ja) * 2004-03-26 2005-10-06 Univ Nagoya カーボンナノチューブの作製方法、及びカーボンナノチューブの作製用基板
JP2010192245A (ja) * 2009-02-18 2010-09-02 Nec Corp エミッタの製造方法、エミッタ、電界放出発光素子の製造方法、電界放出発光素子及び照明装置
JP2012176856A (ja) * 2011-02-25 2012-09-13 Tokyo Electron Ltd カーボンナノチューブの形成方法、その前処理方法、電子放出素子及び照明装置
JP2013540683A (ja) * 2010-09-14 2013-11-07 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー 成長したカーボン・ナノチューブを有するガラス基材及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002542136A (ja) * 1999-04-16 2002-12-10 コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション 多層炭素ナノチューブフィルム
JP2003510462A (ja) * 1999-09-29 2003-03-18 エレクトロファク，ファブリカツィオーン エレクトロテクニシャー スペツィアラルティクテル ゲゼルシャフト ミット ベシュレンクテル ハフツング 基材上にナノチューブ層を生成する方法
JP2005272284A (ja) * 2004-03-26 2005-10-06 Univ Nagoya カーボンナノチューブの作製方法、及びカーボンナノチューブの作製用基板
JP2010192245A (ja) * 2009-02-18 2010-09-02 Nec Corp エミッタの製造方法、エミッタ、電界放出発光素子の製造方法、電界放出発光素子及び照明装置
JP2013540683A (ja) * 2010-09-14 2013-11-07 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー 成長したカーボン・ナノチューブを有するガラス基材及びその製造方法
JP2012176856A (ja) * 2011-02-25 2012-09-13 Tokyo Electron Ltd カーボンナノチューブの形成方法、その前処理方法、電子放出素子及び照明装置

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