JP2008255003A - カーバイド誘導炭素を利用したカーボンナノチューブ混成体とその製造方法、それを含む電子放出源及び前記電子放出源を備えた電子放出素子 - Google Patents
カーバイド誘導炭素を利用したカーボンナノチューブ混成体とその製造方法、それを含む電子放出源及び前記電子放出源を備えた電子放出素子 Download PDFInfo
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- 229910021401 carbide-derived carbon Inorganic materials 0.000 title claims abstract description 110
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 230000005684 electric field Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
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- 239000005977 Ethylene Substances 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- 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
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/30—Cold cathodes, e.g. field-emissive cathode
- H01J1/304—Field-emissive cathodes
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30446—Field emission cathodes characterised by the emitter material
- H01J2201/30453—Carbon types
- H01J2201/30469—Carbon nanotubes (CNTs)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Abstract
【解決手段】カーバイド化合物をハロゲン族元素含有気体と反応させて、カーバイド化合物内の炭素以外の残りの元素を抽出することによって製造されたカーバイド誘導炭素と、カーバイド誘導炭素に担持された金属またはカーバイド誘導炭素に残留する金属と、カーボンソースとの反応によって得られたカーボンナノチューブ混成体であって、カーボンナノチューブ混成体が、カーバイド誘導炭素とそれから成長したカーボンナノチューブとを含むカーボンナノチューブ混成体である。
【選択図】図1A
Description
炭素前駆体であって、平均粒径0.7μmであるα−SiC 100gを使用して、グラファイト反応チャンバ、トランスフォーマで構成された高温電気炉を利用して、1000℃で分当たり0.5リットルのCl2ガスを流して反応を7時間維持することにより、Siを前駆体から抽出することによってカーバイド誘導炭素30gを製造した。
光源:Arレーザ
レーザ出力:20〜30mW
レーザ波長:514.5nm
露光時間(測定):120秒
ビームホール:100μm
1)試料容器内のHeを除去する。
2)装置内に窒素ガスを注入して圧力を記録する。
3)試料容器部分を液体窒素が含まれている容器に入れ、吸着実験中液体窒素の水位を表示された部分に維持するために、実験中に液体窒素を添加し続ける(77K 維持)。
4)試料容器内に窒素を入れて平衡圧力を記録する。
5)装置内の圧力を少しずつ増加させながら2)〜4)を繰り返す。
(0.03〜0.3atmの間で5つ〜6つの平衡圧力値を得る。)
6)液体窒素除去後、常温で30分間真空排気する。
7)試料が入っている試料容器の質量を測定する。
8)各粉末試料に対して全処理と吸着実験過程を繰り返す。
<測定条件>
試料重量(Loading量):0.3〜0.5g
平衡時間:10秒
自動脱気(Automatic Degas)
冷却浴温度(Analysis Bath Temp.):−195.8℃
出発カーバイド化合物であって、平均粒径が3μmであるニッケルカーバイド(Ni3C)100gを使用して500℃で2時間熱化学反応させたことを除いては、実施例1と同じ方法によってカーバイド誘導炭素9.5gを製造し、前記カーバイド誘導炭素に対するラマンピーク分析結果、IG/ID値が約1〜1.3であり、XRD上で2θ=25°でグラファイト(002)面の広いシングルピークが現れた。また、合成後比表面積は、1200m2/gの値を示した。
カーバイド誘導炭素の製造時に出発カーバイド化合物であって、平均粒径が5μmであるZrC100gを使用して600℃で5時間熱化学反応させたことを除いては、実施例1と同じ方法によってカーバイド誘導炭素13gを製造し、前記カーバイド誘導炭素に対するラマンピーク分析結果、IG/ID値が約1〜1.3であり、XRD上で2θ=25°でグラファイト(002)面の広いシングルピークが現れた。また、合成後比表面積は、1200m2/gの値を示した。
カーバイド誘導炭素の製造時に出発カーバイド化合物であって、平均粒径が325meshであるAl4C3 100gを使用して700℃で5時間熱化学反応させたことを除いては、実施例1と同じ方法によってカーバイド誘導炭素25gを製造し、前記カーバイド誘導炭素に対するラマンピーク分析及びX線回折結果、IG/ID値が約1〜3.2であり、2θ=25°でグラファイト(002)面の広いシングルピークが現れ、高解像度TEMの分析結果、多量のグラファイトフリンジが観察された。そのイメージを図9に示した。また、合成後比表面積は、1050〜1100m2/gの値を示した。
カーバイド誘導炭素の製造時に出発カーバイド化合物であって、平均粒径が0.8μmであるB4C 100gを使用して1000℃で3時間反応させたことを除いては、実施例1と同じ方法によってカーバイド誘導炭素を製造し、前記カーバイド誘導炭素に対するラマンピーク分析及びX線回折分析IG/ID値が約0.4〜1であり、2θ=25°でグラファイト(002)面の弱ピークが現れ、高解像度TEMの分析結果、非晶質の開口からグラファイトフリンジに部分的に遷移される過程の形態が観察された。そのイメージを図10に表した。また、合成後比表面積は、1310m2/gの値を示した。
前記実施例1によって得たCNT混成体1g、アクリレートバインダー6.5g、エトキシレートトリメチロールプロパントリアクリレート5.5g、テキサノール5.5g、光開始剤1g及び可塑剤としてジオクチルフタレート1gを混合した後、3ロールミルを使用して均一なペースト状の電子放出源形成用組成物を得るまで混錬した(8回反復)。得られた組成物をITO電極がコーティングされた透明ガラス基板にスクリーン印刷し(10×10mm)、露光(500mJ)及び現像した後、450℃の窒素雰囲気下で焼成し、活性化過程を経てIV測定用冷陰極カソードを製造した。前記冷陰極カソードに、100μmの厚さのポリエチレンテレフタレートフィルムをスペーサで、銅プレートをアノード電極として使用して電子放出素子を製作した。
120 カソード電極
130 絶縁体層
140 ゲート電極
160 電子放出源
169 電子放出源ホール
170 蛍光体層
180 アノード電極
190 上面基板
192 スペーサ
200 電子放出素子
201 上板
202 下板
210 発光空間
Claims (13)
- カーバイド化合物をハロゲン族元素含有気体と反応させて、前記カーバイド化合物内の炭素以外の残りの元素を抽出することによって製造されたカーバイド誘導炭素と、前記カーバイド誘導炭素に担持された金属または前記カーバイド誘導炭素に残留する金属と、カーボンソースとの反応によって得られたカーボンナノチューブ混成体であって、
前記カーボンナノチューブ混成体が、前記カーバイド誘導炭素と当該カーバイド誘導炭素から成長したカーボンナノチューブとを含むことを特徴とするカーボンナノチューブ混成体。 - 前記金属は、Ni、Co、Fe、またはWであり、
前記金属の含量が、前記金属と前記カーバイド誘導炭素との総含量100質量部を基準として0.1から20質量部であることを特徴とする請求項1に記載のカーボンナノチューブ混成体。 - 前記カーボンナノチューブは、一方向に成長するか、またはランダムに成長することを特徴とする請求項1に記載のカーボンナノチューブ混成体。
- 前記カーボンナノチューブは、鉛直方向上向きに成長することを特徴とする請求項3に記載のカーボンナノチューブ混成体。
- 前記カーバイド誘導炭素は、ラマンピーク分析時に1350cm−1での無秩序−誘導された(disordered−induced)Dバンドに対する1590cm−1でのグラファイトGバンドの強度比率が0.3から5の範囲にあることを特徴とする請求項1に記載のカーボンナノチューブ混成体。
- 前記カーバイド誘導炭素のBET比表面積は、950m2/g以上であることを特徴とする請求項1に記載のカーボンナノチューブ混成体。
- 前記カーバイド誘導炭素のX線回折分析結果、2θ=25°でグラファイト(002)面の弱ピークまたは広いシングルピークが現れることを特徴とする請求項1に記載のカーボンナノチューブ混成体。
- 前記カーバイド誘導炭素の電子顕微鏡分析結果、電子回折パターンが非晶質炭素のハロパターンを表すことを特徴とする請求項1に記載のカーボンナノチューブ混成体。
- 前記カーバイド化合物は、SiC4、B4C、TiC、ZrCx、Al4C3、CaC2、チタンタンタルカーバイド、モリブデンタングステンカーバイド、チタンカーボナイトライド、及びジルコニウムカーボナイトライドからなる郡から選択された少なくとも一つのカーバイド化合物であることを特徴とする請求項1に記載のカーボンナノチューブ混成体。
- カーバイド化合物をハロゲン族元素含有気体と反応させた上で、前記カーバイド化合物内の炭素以外の残りの元素を抽出してカーバイド誘導炭素を得る工程と、
前記カーバイド誘導炭素に金属含有化合物を付加し、かつこれらを混合して水素還元反応を実施して、金属が担持されたカーバイド誘導炭素を得る工程と、
前記工程により得たカーバイド誘導炭素とカーボンソースとを反応して、請求項1から9のうち何れか1項に記載のカーボンナノチューブ混成体を得る工程と、
を含むことを特徴とするカーボンナノチューブ混成体の製造方法。 - カーバイド化合物をハロゲン族元素含有気体と反応させた上で、前記カーバイド化合物内の炭素以外の残りの元素を抽出して、前記カーバイド化合物内の金属が残留されたカーバイド誘導炭素を得る工程と、
前記工程によって得た結果物とカーボンソースとを反応して、請求項1から9のうち何れか1項に記載のカーボンナノチューブ混成体を得る工程と、
を含むことを特徴とするカーボンナノチューブ混成体の製造方法。 - 請求項1から9のうち何れか1項に記載のカーボンナノチューブ混成体を含む電子放出源。
- 請求項12に記載の電子放出源を備えた電子放出素子。
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US9957456B2 (en) | 2012-11-20 | 2018-05-01 | Ksm Co., Ltd. | Carbon layer derived from carbide ceramics and preparation method thereof |
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KR101472313B1 (ko) * | 2014-10-01 | 2014-12-15 | 고려대학교 산학협력단 | 탄화물 세라믹스로부터 유도된 탄소층 및 이의 제조방법 |
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US20080248310A1 (en) | 2008-10-09 |
CN101279732A (zh) | 2008-10-08 |
EP1977999A1 (en) | 2008-10-08 |
US7678452B2 (en) | 2010-03-16 |
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