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五、發明說明（1) 【發明所屬之技術領域】 特別涉及一種 本發明涉及一種奈米碳管之製備方法 筆直奈米碳管之製備方法。 【先前技術】 々按，奈米碳管係一種由碳原子組成之直徑為旦 之官狀物，在奈米碳管石墨層中央部份都係六元環/，、=， 末端或轉折部份則有五元環或七元環。奈米碳管係在" 年由n]ima在電弧放電之產物中首次被發現的，具體灸1 文獻Nature，ν〇1·354，ρ·56(1991)。奈米碳管之特_殊> 社見 構決定其具有優良之綜合力學性能，如高彈性模量及低 度’以及優異之電學性能、熱學性能及吸附性能。隨著二 米碳管之長度、直徑及螺旋方式之變化，奈米碳管$呈^ 出金屬性或半導體性質，其中，金屬型奈米碳管本身可作 為一種刀子型金屬導線而在奈米電子學、材料科學等領域 中發揮重要作用。 ' 3 目前製備奈米碳管之方法主要有電弧放電法、脈衝雷 射蒸發法及化學氣相沈積法幾種。電弧放電及脈衝雷射蒸 發法形成之奈米碳管有以下缺點：（丨）奈米碳管產量較… 低，（2 )奈米碳管係與其他碳奈米顆粒混雜在一起，因此 造成奈米碳管純度很低，還需要複雜之淨化工藝，增加製 造成本；（3 )奈米碳管之生長方向無法控制，所形成之奈 米被管呈無序混亂狀’難於工業上作為分子型金屬導線實 際應用。故，目前形成有序奈米碳管陣列之方法主要係化 學氣相沈積法。化學氣相沈積主要係運用奈米尺度之過渡V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) [Technical Field to Which the Invention Is Applicable] In particular, the present invention relates to a method for preparing a carbon nanotube. A method for preparing a straight carbon nanotube. [Prior Art] 々 Press, the carbon nanotube is a kind of officially composed of carbon atoms, and the central part of the graphite layer of the carbon nanotube is a six-membered ring /, , =, end or turning There are five-membered or seven-membered rings. The carbon nanotube system was first discovered in the product of arc discharge by n]ima, the specific moxibustion 1 literature Nature, ν〇1·354, ρ·56 (1991). The characteristics of the carbon nanotubes are determined by the company's comprehensive mechanical properties such as high modulus of elasticity and lowness, as well as excellent electrical, thermal and adsorption properties. With the change of the length, diameter and spiral mode of the two-meter carbon tube, the carbon nanotubes are metallic or semi-conducting. Among them, the metal-type carbon nanotubes themselves can be used as a knife-type metal wire in the nanometer. It plays an important role in the fields of electronics and materials science. ' 3 At present, there are several methods for preparing carbon nanotubes, such as arc discharge method, pulsed laser evaporation method and chemical vapor deposition method. The carbon nanotubes formed by arc discharge and pulsed laser evaporation have the following disadvantages: (丨) the production of carbon nanotubes is lower than..., (2) the carbon nanotubes are mixed with other carbon nanoparticles, thus causing The purity of the carbon nanotubes is very low, and complicated purification processes are required to increase the manufacturing cost. (3) The growth direction of the carbon nanotubes cannot be controlled, and the formed nanotubes are disordered and disordered. Type metal wire is actually used. Therefore, the current methods for forming ordered carbon nanotube arrays are mainly chemical vapor deposition. Chemical vapor deposition mainly uses the transition of nanoscale
1251250 五、發明說明（2) 金屬或其氧化物及其合金作為觸媒，在相對較低之溫度下 熱解含碳之氣體來製備奈米碳管陣列。 5月參閱文獻 Self 〜oriented regular arrays of carbon nanotubes and their field emission properties' Science， Vol.283， P.512〜514(1999)，范 守善等人所提供一種奈米碳管之製備方法為：〇)首先提 供一多孔石夕基底，其孔徑大約為3奈米；（2 )藉掩模板用電 子束蒸發法在基底上形成一層具有規則圖案之觸媒層； (3)將沈積有觸媒層之基底在空氣中於3〇〇它退火；（4)將 基底放在石英反應舟内送入石英管反應爐之中央反應室 中’在氬氣之保護下，將反應爐加熱到7 〇 〇它；（5 )通入 流量為100〇sccm之乙烯氣體，反應15〜6〇分鐘；（6)將反應 爐冷部到室溫，有序奈米碳管陣列即形成於基底之觸媒區 域，並垂直於基底。 々惟’藉由上述製法獲得之奈米碳管在微結構上具有缺 ’即由於其製備初期之熱不穩定及五元碳環及七元碳環 =存在而導致奈米碳管彎曲，從而降低其導電性，使其在 實際工業應用中作為分子型金屬導線而存在困難。故，為 1保奈米碳管作為分子型金屬導線時優良的導電性，必須 提供一種筆直奈米碳管之製備方法。 有蓉於此’提供一種筆直奈米碳管之製備方法實為必 【内容】 為解決先前技術之奈米碳管在微結構上具有缺陷之問1251250 V. INSTRUCTIONS (2) A metal or its oxide and its alloy act as a catalyst to pyrolyze a carbon-containing gas at a relatively low temperature to prepare a carbon nanotube array. May, reference to the literature Self-oriented regular arrays of carbon nanotubes and their field emission properties' Science, Vol. 283, P.512~514 (1999), Fan Shoushan et al. provide a method for preparing a carbon nanotube: 〇) Firstly, a porous stone substrate having a pore diameter of about 3 nm is provided; (2) a catalyst layer having a regular pattern is formed on the substrate by electron beam evaporation using a mask; (3) a catalyst layer is deposited. The substrate is annealed in air at 3 ;; (4) the substrate is placed in a quartz reaction boat and sent to the central reaction chamber of the quartz tube reactor. Under the protection of argon, the reactor is heated to 7 〇〇. (5) introducing an ethylene gas having a flow rate of 100 〇sccm for 15 to 6 minutes; (6) passing the cold portion of the reaction chamber to room temperature, and the ordered carbon nanotube array is formed on the catalyst region of the substrate. And perpendicular to the substrate. 々 ' 'The carbon nanotubes obtained by the above-mentioned method have defects in the microstructure], that is, the carbon nanotubes are bent due to the thermal instability in the initial stage of preparation and the presence of the five-membered carbon ring and the seven-membered carbon ring. Reducing its electrical conductivity makes it difficult to use it as a molecular metal wire in practical industrial applications. Therefore, in order to obtain excellent conductivity of a carbon nanotube as a molecular metal wire, it is necessary to provide a method for preparing a straight carbon nanotube. It is necessary to provide a method for preparing a straight carbon nanotube. [Contents] To solve the defects in the microstructure of the prior art carbon nanotubes
1251250 五、發明說明（3) $ ’本舍明之目的在於提供一種筆直奈米碳管之製備方 法。 為貫現本發明之目# ’本發明提供一種筆直奈米碳管 =m ΐ ’其包括：提供一平滑基底；將磁性觸媒沈積 :该基底^於該基底之上方一定距離處設置磁性元 件，通入石反源^進行反應，奈米碳管從該基底上長出。 才”支術，本發明於生長奈米碳管之基底之上 方疋距離處没置磁性开杜，分义- . 長過程中所產生之磁場對磁^ ^*米故官之生 夂来瑞營，墟保太止荨現象之產生，從而獲得筆直 $導電性能。…、奴官作為分子型金屬導線應用時優良 【實施方式】 括下列步j弟步：丨!本：：提：之奈米碳管之製備方法包 離處設置磁性元件；+驟/4驟1f於該基底之上方一定距 碳管從該基底上長出。 通入碳源氣進行反應，奈米 請一併參閱第二圖及笙二 ^ 碳管之製備方法進一步詳細；；；…明所提供之奈米 為J先…實施例中使用…晶片作 - 該基片亦可選用N型矽晶片、本徵矽晶片 1251250 五、發明說明（4) — ---- 或表面有一氧化矽層之矽晶片。 其次’將磁性觸媒6沈積於平滑基底3表面。將磁性金 屬利用電子束蒸發沈積法、#沈積法或_射法等方法形成 ，平滑基底3上；將沈積有磁性金屬之平滑基底3放置於空 氣中，於30 0〜40 0 °C熱處理約1〇小時，使磁性金屬氧化成 金屬氧化物顆粒（圖未示）；將其用還原性氣體還原成奈米 級磁性觸媒6 ;再將處理後之平滑基底3切割成矩形。其 中，磁性金屬可為鐵（pe)、始（C〇)、鎳（^丨）或其合金之 一，本實施例中選用鐵；所述磁性金屬之沈積厚度為幾奈 米到幾百奈米，以5奈米為較佳；還原性氣體可為氫氣或 氨氣等。 然後’於平滑基底3之上方一定距離處設置磁性元 件。將其中一片矩形平滑基底3裝入反應舟2中，將反應舟 2送入管狀石英爐之中央反應室1中，於反應室1上方、平 滑基底3之相對面設置磁性元件，並使該磁性元件與平滑 基底3相距一預定距離。在本實施例中，磁性元件為一纏 繞在柱狀體7上之螺旋形線圈5，向螺旋形線圈5中通入一 預定電流’向反應室1内通入保護氣體並加熱至一預定溫 度。其中，該保護氣體可為惰性氣體或氮氣，本實施例中 選用氬氣；該預定溫度因磁性觸媒材料之不同而不同，當 選用金屬鐵為觸媒金屬時，則_般加熱到5 〇 〇〜7 〇 〇 ^，以 6 50 °C為較佳；向螺旋形線圈5内通入一預定電流之動作亦 可在通入保濩氣體後為之；磁性元件亦可使用磁鐵等复他 具有磁性可吸引磁性觸媒之元件。1251250 V. INSTRUCTIONS (3) $' The purpose of Benming is to provide a method for preparing a straight carbon nanotube. For the purpose of the present invention, the present invention provides a straight carbon nanotube=m ΐ 'which includes: providing a smooth substrate; depositing a magnetic catalyst: the substrate is provided with a magnetic element at a distance above the substrate The reaction is carried out by the stone source, and the carbon nanotubes grow from the substrate. Only in this case, the invention has no magnetic opening at the distance above the base of the growing carbon nanotubes, and the meaning of the magnetic field generated during the long process is the magnetic ^ ^ * m Camp, the market is too long to stop the phenomenon, so as to obtain straight $ conductive performance...., slaves as a molecular metal wire application is excellent [implementation] including the following steps j step: 丨! Ben:: mention: The preparation method of the carbon tube is provided with a magnetic element from the periphery; + the step / 4 step 1f is formed from the substrate from the carbon tube above the substrate. The carbon source gas is used for the reaction, and the nanometer is referred to the same. The preparation method of the second figure and the second carbon tube is further detailed;;;...the nanometer provided by the invention is J first...the embodiment is used...the wafer is used - the substrate can also be selected from the N-type wafer, the intrinsic wafer 1251250 V. INSTRUCTION DESCRIPTION (4) — ---- or a germanium wafer with a hafnium oxide layer on the surface. Next, 'the magnetic catalyst 6 is deposited on the surface of the smooth substrate 3. The magnetic metal is deposited by electron beam evaporation, #deposition Or _shooting method, etc., smoothing the substrate 3; depositing magnetic The smooth substrate 3 of the genus is placed in the air and heat-treated at 30 0 to 40 ° C for about 1 hour to oxidize the magnetic metal into metal oxide particles (not shown); it is reduced to nanometer level with a reducing gas. The magnetic catalyst 6 is further processed into a rectangular shape by processing the smooth substrate 3, wherein the magnetic metal may be one of iron (pe), initial (C〇), nickel (^丨) or an alloy thereof, and is selected in the embodiment. Iron; the magnetic metal has a deposition thickness of several nanometers to several hundred nanometers, preferably 5 nanometers; the reducing gas may be hydrogen gas or ammonia gas, etc. Then 'set at a certain distance above the smooth substrate 3 a magnetic element: one of the rectangular smooth substrates 3 is loaded into the reaction boat 2, and the reaction boat 2 is sent into the central reaction chamber 1 of the tubular quartz furnace, and magnetic elements are disposed above the reaction chamber 1 on the opposite side of the smooth substrate 3, and The magnetic element is spaced apart from the smooth substrate 3 by a predetermined distance. In the present embodiment, the magnetic element is a spiral coil 5 wound around the columnar body 7, and a predetermined current is passed into the spiral coil 5 to react. Passing protective gas into chamber 1 and heating to a predetermined temperature, wherein the shielding gas may be an inert gas or a nitrogen gas, and argon gas is selected in the embodiment; the predetermined temperature is different depending on the magnetic catalyst material, and when metal iron is selected as the catalytic metal, the heating is performed. Up to 5 〇〇~7 〇〇^, preferably 6 50 °C; the action of introducing a predetermined current into the spiral coil 5 can also be performed after the gas is supplied; the magnetic element can also use a magnet He has the magnetic component that attracts the magnetic catalyst.
1251250 、發明說明（5) 最，，通入碳源氣進行反應，奈米碳管7從 ^ 上長出並垂直於平滑基底3。盆 尸/月基底3 物’包括乙炔、乙掄笼,人源亂為峡氣化合 乙烯專，本貫施例中選用乙炔。 戶、也歹I中係於反應室上方之基底3之上一 ^ 處設ί二螺if形線圈5，控制通入螺旋形線圈5之電：*離 :二i Λ螺旋形線圈5之距離及磁性觸媒6之粒二， 1性觸媒6在通電之螺旋形線圈5之：大小 身重力及奈米碳管7之支撐力之共同作用 力、自 管7垂直基底3並向基底3之上方 冷不米碳 吸引作用，可克服夺米碳总H/、由於上述磁場力之 之彎曲現象，並可防止在奈-二不％、疋而造成 元環及七元環等微結構缺陷現^ : 兀％構造中摻雜五 w奶丨曰現象之產生， 米碳管7。 攸而獲仔筆直奈 相較於先前技術，本發 方一疋距離處設置磁性元件 長過程中所產生之磁場對磁 Ά垂直基底之方向生長，防 構造中推雜五元環及七元環 奈米碳管，確保奈米碳管作 的導電性能。t 綜上所述，本發明確已 提出專利申請。惟，以上所 例，自不能以此限制本案之 技藝之人士援依本案之發明 明於生長奈米碳管之基底之上 ’該磁性元件於奈米碳管之生 性觸媒之作用會引導奈米碳管 止奈米碳管彎曲及在其六元環 等現象之產生，從而獲得筆直 為分子型金屬導線應用時優良 符合發明專利之要件，遂依法 述者僅為本發明之較佳實施 申請專利範圍。舉凡熟悉本案 精神所作之等效修飾或變化，1251250, invention description (5) Most, the carbon source gas is introduced for reaction, and the carbon nanotube 7 grows from ^ and is perpendicular to the smooth substrate 3. The pelvis/month base 3 includes acetylene and acetamidine cages, and the human source is chaotic gas and ethylene. The acetylene is used in the present example. In the household, the 歹I is placed on the base 3 above the reaction chamber, and the 螺 two-spiral if-coil 5 is controlled to control the electric power of the spiral coil 5: * from: the distance of the two spiral coils 5 And the magnetic catalyst 6 of the particle 2, the 1st catalyst 6 in the energized spiral coil 5: the combined force of the body and the gravity and the supporting force of the carbon nanotube 7, from the tube 7 vertical base 3 and to the base 3 Above the cold non-meter carbon attracting effect, it can overcome the total H/ of the rice, the bending phenomenon due to the above magnetic force, and prevent the micro-structure defects such as the meta-ring and the seven-membered ring caused by the nano-two Now ^ : 兀% structure in the doping of five w milk thistle phenomenon, carbon nanotubes 7.攸 攸 获 获 获 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本The carbon nanotubes ensure the conductivity of the carbon nanotubes. t In summary, the present invention has indeed filed a patent application. However, in the above example, the person who can't limit the skill of the case can help the invention according to the case to be on the base of the growing carbon nanotube. The role of the magnetic element in the biocatalyst of the carbon nanotube will guide Nai. The carbon nanotubes are resistant to the bending of the carbon nanotubes and the occurrence of the phenomenon of the six-membered ring, so that the application of the straight-line metal wire is excellent in accordance with the requirements of the invention patent, and the method according to the law is only the preferred application of the invention. Patent scope. Anyone who is familiar with the equivalent modification or change of the spirit of the case,
1251250 五、發明說明（6) 皆應涵蓋於以下申請專利範圍内。 第10頁 1251250 圖式簡單說明 第一圖係本發明之CVD法製備奈米碳管之流程圖。 第二圖係本發明之CVD法生長奈米碳管前之示意圖。 第三圖係本發明之CVD法獲得之奈米碳管之示意圖。 【主要元件符號說明】 中央反應室 1 反應舟 2 基底 3 柱狀體 4 螺旋形線圈 5 磁性觸媒 奈米碳管 71251250 V. The invention description (6) should be covered by the following patent application. Page 10 1251250 BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a flow chart of the preparation of a carbon nanotube by the CVD method of the present invention. The second figure is a schematic diagram of the CVD method of the present invention before the growth of the carbon nanotubes. The third figure is a schematic diagram of a carbon nanotube obtained by the CVD method of the present invention. [Main component symbol description] Central reaction chamber 1 Reaction boat 2 Base 3 Columnar 4 Spiral coil 5 Magnetic catalyst Carbon nanotube 7
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