1314917 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種奈米碳管陣列之製備方法，尤其涉及—種製 奈米碳管陣列之製備方法。 【先前技術】 -由於奈米碳管獨特之電學性質，其於奈米積體電路、單分子器件等領 域之應用有著不可估量之前景。目前人們已經能夠實驗製造基於奈米碳^ 之場效應管、反或閘等器件。隨著奈求碳f之應用，合成大面積^米二 管陣列方面也已取得很大之進展，並有望應用於場發射平板顯示器=設備 中。 籲目前製備絲碳管之綠主要有電弧放電法、脈衝雷聽發法及化學 氣相沈積法三種。電弧放電及脈衝t射蒸發法形成奈米碳管有二下幾個ς 點：（1)奈米碳管產量較低；（2)奈米碳管與其他奈来碳顆粒混雜在一起，因 此造成奈米碳管之純度很低，還需要複雜之淨化工藝，增加製造成本 奈米碳管之生長方向無法控制，所形成之奈米碳管無序混亂，難以於工業 上應用。而形成有序奈米碳管_之方法目社要為化學氣相沈積法。化 學氣相沈積主要係顧奈米尺度之過渡金屬或其氧化物作為催化劑，於相 對低之溫度下熱解含碳源氣體來製備奈米碳管陣列。 ri^##A^^^Science,Vol.283, 512-514(1999),Self-oriented regular • arrays of carbon nan〇tubes and their field emissi〇n pr〇perties一文中揭露一種 奈米碳管陣列之製備方法：首先提供—多孔錄底，其孔徑大約為3奈米； 然後通過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鐵催化 劑層，將沈積有鐵催化劑層之基底在空氣中3〇(rc退火；將基底放入石英反 應舟裏並送人反應爐之中央反魅中’於氬氣之保護下，將基底加熱到獨 。(:後’以1000標準立方爱米每分鐘(sccm)之流量通入乙稀氣體，反應15 6〇 分鐘；於基底上具有鐵催侧之區域將生長出—有序奈米碳辨列，且奈 米碳管陣列中之奈米碳管基本垂直於基底。然，因為奈来碳管生長過程中， 無定型碳會同時沈積於奈米碳管之外表面，使奈米碳管之間之范德華力降 低。故依該法生長出之奈米碳管陣列中之奈米碳管之職德華力較弱，從 1314917 過程中’石英爐内之壓強可保持為760托。於本實施例之常壓化學氣相沈積 法製備奈米碳管陣列過程中，應注意控制反應氣體中碳源氣與載氣之流量 使％源氣與載氣之流量比不高於1〇%且高於〇_ 1%為宜。反應氣體中碳源 氣^含量決定無定型碳之沈積速度，即碳源氣與載氣之摩爾比越低，無定 ΐ碳積速度越慢。因此，本實施例中通過控制反應氣體中碳源氣與載 氣之流量，可使碳源氣與載氣之摩爾比低於狨。這樣可使無定型碳之沈積 速度減慢，獲得具有乾淨表面之奈米碳管，且奈米碳管之間之范德華力較 大。通過這錄強之織華力使絲碳管結合成穩定之束狀。 第二實施例 本實施例是採用低壓化學氣相沈積法進行奈米碳管陣列之製備。通 常，低壓化學氣相沈積法之壓強範圍為。本實施例中，選 用拋光之判為基底，翻鐵作為催化劑，選用乙炔為反應氣體。將鐵催 =通過磁控麵法’以Q. Q1奈米/秒之沈積速率在抛光抑基底上形成厚 又為3〜6奈米之鐵催化劑層。將該形成有鐵催化劑層之基底放人一石英爐 中’並加熱至680〜720攝氏度。向石英爐中以施卿之流量通入乙快，並 保持10’分鐘左右；轴可獲得—奈米碳管陣列。其中，於奈米碳管陣列 程中，石英爐内之壓強可保持為2托。於本實施例之低壓化學氣相 =1長過程中’反應氣體可全部選用碳源氣而不需要載氣，或通入少 二根據氣體在不同壓強下之自身性f，隨壓強將低，氣體之密 因而低壓下製備奈米碳管時需要通人大量之碳源氣。如第 =平不2足本實施例之條件下，生長結束即可獲得超順排列 該超順排狀奈米碳管_，可峨中拉出奈 /厌&、’、，以使將該奈米碳管線應用到宏觀領域中。 可以理解’本第-及第二實施例巾其壓強並 細^ :=:r之流量比等，於任何範圍之壓強下二= 綜上所述’本發明確已符合發明專利要件，爱依 往 述者僅為本發明之她實施例，舉凡熟 1依 本案發明精神所作之等效修飾或變化，嫩含於以下之it細&内 1314917 【圖式簡單說明】 之奈米碳管陣 列之 TEM(Transmission 第一圖係先前技術生長& Electron Microscope)照片。 奈米ί管==1^/。_例提供之奈米碳管陣列之製備方法生長出之 ^第二圖係本發明實施例提供之奈米碳管陣狀製備方法生長出 之奈米 戈 ί 陣列之HRTEM (High Resolution Transmission Electron Microscope) 照片。1314917 IX. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a carbon nanotube array, and more particularly to a method for preparing a carbon nanotube array. [Prior Art] - Due to the unique electrical properties of carbon nanotubes, its application in the field of nano-integrated circuits, single-molecule devices, etc. has an inestimable prospect. At present, people have been able to experimentally manufacture devices based on nano-carbon nanotubes, FETs, or gates. With the application of carbon, the development of large-area two-tube arrays has also made great progress, and is expected to be applied to field emission flat panel display devices. At present, there are three main types of green carbon fiber tubes, such as arc discharge method, pulsed lightning method and chemical vapor deposition method. There are two points in the formation of carbon nanotubes by arc discharge and pulsed e-evaporation: (1) the carbon nanotube output is low; (2) the carbon nanotubes are mixed with other nai carbon particles, so The purity of the carbon nanotubes is very low, and a complicated purification process is required, which increases the manufacturing cost. The growth direction of the carbon nanotubes cannot be controlled, and the formed carbon nanotubes are disorderly disordered and difficult to be industrially applied. The method of forming ordered carbon nanotubes is to be a chemical vapor deposition method. Chemical vapor deposition is mainly carried out by using a Guyn-scale transition metal or its oxide as a catalyst to pyrolyze a carbon-containing source gas at a relatively low temperature to prepare a carbon nanotube array. Ri^##A^^^Science, Vol.283, 512-514(1999), Self-oriented regular • arrays of carbon nan〇tubes and their field emissi〇n pr〇perties, a nanocarbon tube array The preparation method comprises the following steps: firstly providing a porous recording substrate having a pore diameter of about 3 nm; then forming an iron catalyst layer having a regular pattern on the substrate by electron beam evaporation through a mask, and depositing the substrate on which the iron catalyst layer is deposited 3 空气 in the air (rc annealing; put the substrate into the quartz reaction boat and send it to the central anti-enchantment of the reactor) under the protection of argon, heat the substrate to the sole. (: After '1000 standard cubic meters of rice The flow rate per minute (sccm) is passed into the ethylene gas for 15 6 minutes; the area with the iron side on the substrate will grow - the ordered nanocarbon is identified, and the nanometer in the carbon nanotube array The carbon tube is substantially perpendicular to the substrate. However, because the carbon nanotubes are deposited on the outer surface of the carbon nanotubes during the growth of the carbon nanotubes, the van der Waals force between the carbon nanotubes is reduced. The role of the carbon nanotubes in the carbon nanotube array The force is weak, from the 1314917 process, the pressure in the quartz furnace can be kept at 760 Torr. In the process of preparing the carbon nanotube array by the atmospheric pressure chemical vapor deposition method in this embodiment, attention should be paid to controlling the carbon source gas in the reaction gas. The flow rate of the carrier gas is such that the flow ratio of the source gas to the carrier gas is not higher than 1% and higher than 〇 1%. The carbon source gas content in the reaction gas determines the deposition rate of the amorphous carbon, that is, the carbon source. The lower the molar ratio of gas to carrier gas, the slower the carbon deposition rate is. Therefore, in this embodiment, the molar ratio of carbon source gas to carrier gas can be controlled by controlling the flow rate of carbon source gas and carrier gas in the reaction gas. Lower than 狨. This can slow down the deposition rate of amorphous carbon, obtain a carbon nanotube with a clean surface, and the van der Waals force between the carbon nanotubes is large. The invention combines into a stable bundle. Second Embodiment This embodiment is to prepare a carbon nanotube array by a low pressure chemical vapor deposition method. Generally, the pressure range of the low pressure chemical vapor deposition method is: in this embodiment, the selection is The polishing is judged as the substrate, and the iron is used as a catalyst. Acetylene is the reaction gas. The iron catalyst layer is formed on the polishing substrate by a magnetron surface method at a deposition rate of Q. Q1 nm/sec to form a thick iron catalyst layer of 3 to 6 nm. The substrate of the catalyst layer is placed in a quartz furnace and heated to 680 to 720 degrees Celsius. The flow into the quartz furnace is carried out at a flow rate of Shiqing and maintained for about 10 minutes; the shaft is available as an array of carbon nanotubes. Among them, in the carbon nanotube array process, the pressure in the quartz furnace can be maintained at 2 Torr. In the low pressure chemical vapor phase=1 long process of the present embodiment, the reaction gas can be all selected from the carbon source gas without the carrier gas. According to the self-property f of the gas under different pressures, the pressure will be low, and the gas is dense and thus the carbon nanotubes are required to produce a large amount of carbon source gas at a low pressure. If the condition of the present embodiment is the same as that of the present embodiment, the super-sequential arrangement of the super-sequential carbon nanotubes can be obtained by the end of the growth, and the navel/analysis, and the The nanocarbon pipeline is applied to the macroscopic field. It can be understood that the pressure of the first and second embodiments of the towel and the ratio of the flow ratio of :=:r, etc., under the pressure of any range, two = in summary, the invention has indeed met the requirements of the invention patent, Aiyi The foregoing is only the embodiment of the present invention, and the equivalent modification or variation made by the skilled person in accordance with the spirit of the invention is as follows: the fine carbon nanotube array of the following fine & 1314917 [simple description of the figure] The TEM (Transmission first picture is a prior art growth & Electron Microscope) photo. Nano ^ tube = = 1 ^ /. The second embodiment of the nanocarbon tube array prepared by the embodiment of the present invention is a nano resolution transmission Electron Microscope of the nanogeo array produced by the embodiment of the present invention. ) Photo.
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