1246503 玖、發明說明 内容、實 (發，說明應敘明：發明所屬之技術領域、先前技術 施方式及圖式簡單說明） 【發明領域】 本电明係關於一種奈米碳管生長方法，尤指一種奈米碳管陣列生‘ 方法。 又* 【發明背景】 奈米碳管係一種由碳原子組成之直徑為奈米量級之中空管狀物，在 奈米碳管石墨層中央部分都係六元環，而在末端或轉折部分則有五元環 或七元環。奈米碳管係在1991柏Iijima在電孤放電的產物中首次# 現，發表在1991年出版的Nature 354，56。奈米碳管之特殊結構決定 其具有優良的綜合力學性能，如高彈性模量、高楊氏模量與低密度，以 及優異之電學性能、熱學性能及吸附性能。隨著奈米碳管之長度、直徑 及螺旋方式之變化，絲碳f可呈灿金屬性或半導雖冑。由於奈米 碳管的優異特性，因此可望其在奈米電子學、材料科學、生物學、^匕學 等領域中發揮重要作用。 子 ，目前製備奈米碳管之方法主要有電弧放電法、脈衝雷射蒸發法及春 學氣相沈積法_。電赋電及脈衝雷射紐法形叙奈轉管有以下 幾個缺點.⑴奈米碳管產量較低；⑵奈純管與其他奈麵粒混雜， 以成奈米％1官的純度很低’還需要複雜之淨化卫藝，增加製造成本.⑶ 奈米碳管之生長方向無法控制，所形成之奈米碳f無序絲，難於工業 上應^ °㈣财縣米碳管_財法目社要触學氣相沈積法。 4匕學範相沈積主要係職奈米尺度的過渡金屬或其氧化物作為催化劑， 相對低的'皿度^熱解含碳之源氣體來製備奈米石炭管陣列。 續次H (發明說明頁不敷使用時，請註記並使用續頁） 1246503 發明說明 范守善等人在文獻 Science 283，512-514(1999)，Self-oriented regular arrays of carbon nanotubes and their field emission properties中所描述的製備方法係：首先提供一多孔矽基底，其孔經大 小約為3奈米，然後通過光罩用電子束蒸發法在基底上形成一層具有規 則圖案之催化劑一鐵層，然後將沈積有鐵之基底在空氣中3⑽。匚條件下 退火，然後將基底放在石英反應舟裏送入石英管式反應爐之中央反應室 中，在氬氣保護下，將反應爐加熱到7〇〇它後，以流量1〇〇〇sccm通入乙 烯氣，反應15-60分鐘，然後將反應爐冷卻到室溫，有序奈米碳管陣费 即沈積在基底上含鐵之區域，且奈米碳管垂直於基底。 惟，奈米碳管生長過程中，無定型碳會同時沈積在奈求碳管之外表 面，使奈米碳管之間的凡德瓦爾力降低，故依該法生長所得之奈米碳管 陣列中的奈米碳管之間凡德瓦_力較弱。“圖係依該方法生長所得之 奈米碳管陣列放人二氣乙财超聲侧1G分鐘後之騎好顯微鏡 OEM’ Transmission ElectronMicr〇sc〇pe)照片，由第九圖可看出，超 聲作用後，奈米碳管陣列中奈米碳管已基本分散在二氯乙烧中。鲁 有鑑於此，提供-種改進之奈米碳管陣列生長方法實為必要。 【發明目的] 本發明之目的在於提供—齡米碳轉耻長方法，Μ =管_中的奈料管表面乾淨帽，通軌德㈣力結合成穩料 束狀’即為束狀奈米碳管陣列。 【發明特徵】 本發明奈米辟陣列生長方法包括以下步驟：提供一平滑基底，將 續次頁（㈣朗頁砸科，咖錢用續頁） 7 1246503 發明說明、4賣頁 催化劑沈積⑽基底上，將沈射雜_基餘一 預定溫度後通人麵氣與保護氣體之混合氣體，並且保持慨外^产鱼 環境溫度之溫差在5(TC以上，魏氣之分壓低於，使奈鱗^歹^ 基底長出。該生長出之奈米碳管_為束狀奈米碳#_。 【較佳實施例】 請參閱第-圖，本發明之生長方法包括以下步驟：首先提供一平滑 基底，於其上沈積催化劑，紐進行熱_，預加熱基底後通入混合氣 體長出奈米碳管陣列。 ^ 睛-併蒼閱第二圖與第三圖’首先提供一平滑基底1〇，可選用p型或 N型或曰本_晶片或表面有—層氧化_♦晶片為基底，本發明中選用p 型石夕=或表面有-層氧化㈣％晶片作為基底1()，其為圓形，直徑為 5: 08，米’厚?5。微米’將該基細拋域得平滑基&。將金屬催化義 利^電子束蒸發沈積、熱沈積錢射法等方法形餅該基底上，其厚度 為幾^到幾百奈米，其中金屬催化劑2〇可為鐵(Fe)、钻(Co)、_^ 或/、5至之，本貫施例選用鐵為催化劑2〇，沈積厚度為5奈米。 將沈積有催化劑20的基底1〇在空氣中， 於300-400°C之溫度條件下 =、⑽小日t ’使催化舰化成顆粒，然後再將其用氫氣錢氣還原形 成奈米級雛，再將處理後的基底切赋矩形基底10。 、=/、中一片矩形基底10裝入一反應舟中，一般為石英反應舟，將反 3舟裝入管狀石英爐中央的反應室裏，在氣體保護下加熱至-預定溫 ^ :中孩保濩氣體為惰性氣體或氬氣，本實施例選用氬氣，該預定 ’皿度與催化劑有關，當選職為催化劑，則—般—7 為650°c。 k IB續次頁（發明說明頁不敷使用時，請註記並使用續頁） 8 1246503 ~ ——~* 發明說明續頁 · 通入碳源氣與保護氣體的混合氣體，其中碳源氣為碳氫化合物，可 為乙炔、乙烯等，本實施例選用乙炔；該保護氣體為惰性氣體或氤氣，-本實施例選用氬氣。通過控制碳源氣的流量來控制催化劑的局部溫度 Tc，環境溫度直接通過控制石英爐溫度Tl來調節，使催化劑的溫度t與反 應爐中環境溫度TL形成一溫差ΔΤ至少在50°c以上，控制碳源氣與保護氣 體的流量比，使碳源氣之分壓至少在20%以下，優選為分壓在1〇%以 反應5一30分鐘使奈米碳管陣列30從基底上.10長出，如第四圖所示，其掃 描電子顯微鏡照片請參閱第五圖。 ^ 因為奈米碳管生長速度與催化劑溫度和環境溫度的溫差成正比，溫 差越大，奈米碳管生長越快；而無定型碳的沈積速度與碳源氣分壓成正 比，碳源氣分壓越低，無定型碳的沈積速度越慢。故，本發明通過控制 催化劑的溫度Tc與環境溫度Tl的溫差Δτ至少在5(rc以上，使奈米碳^的 生長速度提高；通過調節碳源氣與混合氣體的流量比，使碳源氣得分壓 至少在20%以下’使無定型碳的沈積速度減慢。採用此工藝條件後生長出 的奈米碳管具乾淨光滑之表面，且奈米碳管之間凡德瓦爾力較大，^ 基底為平滑基底，生長出的奈米碳管較在多孔基底上生長出的奈米碳| 更緊密，故，奈米碳管易於因凡德瓦爾力而聚集形成束狀，其透射^ 顯微鏡照片請參閱第六圖所示。 兒 ▲故，採財發明之方法製備的絲碳管_為束狀奈米碳管陣列， 且該束狀結構很穩定，將以本發明之方法生長所得之奈米石炭管陣列在二 乳乙烧中超聲伽1G分鐘，拍得顶⑽，如第七騎示，辦列中的奈 米碳管沒有分散在二氣乙烷中，仍然保持束狀結構。 不 綜上所述，本發明符合發明專利要件，爰依法提出專利申請。惟， 國續次頁（翻麵頁不驗鹏，纖記雌職頁） 1246503 以上所述者僅為本發明之較佳實施例，舉1246503 玖, the description of the invention, the actual description, the description should be clarified: the technical field to which the invention belongs, the prior art application method and the simple description of the drawings. [Invention Field] The present invention relates to a method for growing a carbon nanotube, Refers to a method of producing a carbon nanotube array. [Background of the Invention] The carbon nanotube is a hollow tubular material composed of carbon atoms and having a diameter of the order of nanometers. The central portion of the graphite layer of the carbon nanotube is a six-membered ring, and at the end or the transition portion. There are five or seven yuan rings. The nanocarbon tube system was first published in the product of electric solitary discharge in 1991 by Iijima. Presented in 1991, Nature 354, 56. The special structure of the carbon nanotubes determines its excellent overall mechanical properties, such as high elastic modulus, high Young's modulus and low density, as well as excellent electrical, thermal and adsorption properties. As the length, diameter and spiral pattern of the carbon nanotubes change, the silk carbon f can be made of a metallic or semi-conductive material. Due to the excellent properties of the carbon nanotubes, it is expected to play an important role in the fields of nanoelectronics, materials science, biology, and biology. At present, the methods for preparing carbon nanotubes mainly include arc discharge method, pulsed laser evaporation method and spring vapor deposition method. The electric and pulsed lasers have the following shortcomings: (1) the carbon nanotube output is low; (2) the nai tube is mixed with other nai particles, and the purity of the nanometer is very high. Low' also requires complex purification and maintenance, increasing manufacturing costs. (3) The growth direction of carbon nanotubes can not be controlled, the formation of nano carbon f disordered silk, difficult to industrially ^ ° (four) Caixian rice carbon tube The law school should touch the vapor deposition method. 4 The delineated sedimentary phase is mainly composed of a transition metal of the nanometer scale or its oxide as a catalyst, and a relatively low 'degree of heat> pyrolysis of a carbon-containing source gas to prepare a nano-carboniferous tube array. Continued H (When the description page is not enough, please note and use the continuation page) 1246503 Description of the invention Fan Shoushan et al., Science 283, 512-514 (1999), Self-oriented regular arrays of carbon nanotubes and their field emission properties The preparation method described in the following is: firstly providing a porous tantalum substrate having a pore size of about 3 nm, and then forming a regular pattern of catalyst-iron layer on the substrate by electron beam evaporation through a photomask, and then The substrate on which iron is deposited is 3 (10) in air. Annealing under 匚 conditions, then placing the substrate in a quartz reaction boat into the central reaction chamber of the quartz tube reactor, heating the reactor to 7 Torr under argon protection, and then flowing at 1 Torr. The sccm is passed through ethylene gas for 15 to 60 minutes, and then the reactor is cooled to room temperature, and the ordered carbon nanotubes are deposited on the iron-containing region of the substrate, and the carbon nanotubes are perpendicular to the substrate. However, during the growth of the carbon nanotubes, the amorphous carbon is deposited on the outer surface of the carbon nanotubes at the same time, so that the van der Waals force between the carbon nanotubes is reduced, so the carbon nanotubes grown according to the method are grown. The van der Waals between the carbon nanotubes in the array is weak. "The picture shows the array of carbon nanotubes grown by this method. The photo of the microscope 'OEM ElectronMicr〇sc〇pe' is taken after 1G minutes on the ultrasonic side of the second gas and the silver side. From the ninth figure, the ultrasonic effect can be seen. After that, the carbon nanotubes in the carbon nanotube array have been substantially dispersed in the dichloroethane. In view of the above, it is necessary to provide an improved nanocarbon tube array growth method. The purpose is to provide an age-old carbon-to-shame method, in which the surface of the tube of the tube is clean, and the surface of the tube is combined with a force beam to form a beam-shaped carbon nanotube array. The nanochip array growth method of the present invention comprises the following steps: providing a smooth substrate, which will be continued on the page ((4) Lange, 咖 咖) 7 1246503 invention description, 4 selling catalyst deposition (10) on the substrate, After the predetermined temperature, the surface of the gas is mixed with the gas of the protective gas, and the temperature difference between the surface temperature of the fish and the fish is kept at 5 (TC or more, and the partial pressure of Wei gas is lower than that, so that the scale is lower than that. ^ The base grows. The growing carbon nanotubes _ Preferred Embodiments Referring to the first embodiment, the growth method of the present invention comprises the steps of first providing a smooth substrate, depositing a catalyst thereon, heating the substrate, and preheating the substrate. Into the mixed gas grows out of the carbon nanotube array. ^ Eye - and the second and third pictures of the 'first provide a smooth substrate 1 〇, you can choose p-type or N-type or 曰 _ wafer or surface has a layer The oxidized _ ♦ wafer is a substrate. In the present invention, a p-type 夕 = = or a surface-layer oxidized (four) % wafer is selected as the substrate 1 (), which is circular, having a diameter of 5:08, and a meter thickness of 5. micron. The base is thinned to a smooth basis & a metal catalyzed electron beam evaporative deposition, a thermal deposition method, and the like are formed on the substrate, and the thickness thereof is several to several hundred nanometers, wherein the metal catalyst 2 The crucible may be iron (Fe), drill (Co), _^ or /, 5 to it. In the present embodiment, iron is used as the catalyst 2〇, and the deposition thickness is 5 nm. The substrate on which the catalyst 20 is deposited is immersed in In the air, at a temperature of 300-400 ° C =, (10) small days t 'to make the catalytic ship into particles, and then use it to hydrogen money The gas is reduced to form a nano-sized chick, and the treated substrate is then cut into a rectangular substrate 10. ???, =, a medium rectangular substrate 10 is loaded into a reaction boat, generally a quartz reaction boat, and the reverse 3 boat is loaded into the tubular quartz. In the reaction chamber in the center of the furnace, under the protection of gas, it is heated to a predetermined temperature: the gas in the middle of the furnace is inert gas or argon gas. In this embodiment, argon gas is selected, and the predetermined degree is related to the catalyst. , then - 7 is 650 ° C. k IB continued page (when the invention page is not enough, please note and use the continuation page) 8 1246503 ~ ——~* Description of the invention Continued page · Access to carbon source gas and The mixed gas of the shielding gas, wherein the carbon source gas is a hydrocarbon, which may be acetylene, ethylene or the like. In the embodiment, acetylene is used; the shielding gas is an inert gas or helium gas, and the argon gas is selected in the embodiment. The local temperature Tc of the catalyst is controlled by controlling the flow rate of the carbon source gas, and the ambient temperature is directly adjusted by controlling the temperature T1 of the quartz furnace, so that the temperature t of the catalyst forms a temperature difference ΔΤ of at least 50 ° C with the ambient temperature TL in the reactor. Controlling the flow ratio of the carbon source gas to the shielding gas so that the partial pressure of the carbon source gas is at least 20% or less, preferably at a partial pressure of 1% to react for 5 to 30 minutes to cause the carbon nanotube array 30 to be removed from the substrate. Growing up, as shown in the fourth figure, see the fifth picture of the scanning electron microscope. ^ Because the growth rate of carbon nanotubes is proportional to the temperature difference between catalyst temperature and ambient temperature, the larger the temperature difference, the faster the carbon nanotube growth; while the deposition rate of amorphous carbon is proportional to the partial pressure of carbon source, carbon source gas The lower the partial pressure, the slower the deposition rate of amorphous carbon. Therefore, the present invention improves the growth rate of the nanocarbon by controlling the temperature difference Δτ of the temperature Tc of the catalyst and the ambient temperature T1 to be at least 5 (rc or more; and adjusting the flow ratio of the carbon source gas to the mixed gas to make the carbon source gas The scoring pressure is at least 20% or less 'the deposition rate of amorphous carbon is slowed down. The carbon nanotubes grown after using this process have a clean and smooth surface, and the van der Waals force between the carbon nanotubes is large. ^ The substrate is a smooth substrate, and the growing carbon nanotubes are tighter than the nanocarbons grown on the porous substrate. Therefore, the carbon nanotubes are easily aggregated by van der Waals force to form a bundle, and the transmission is microscopic. Please refer to the sixth figure for the photo. ▲ ▲ Therefore, the carbon nanotube prepared by the method of the invention is a bundle of bundled carbon nanotubes, and the bundle structure is stable and will be grown by the method of the present invention. The nano-carboniferous tube array was ultrasonically gamified for 1G minutes in the second emulsion, and the top (10) was taken. As shown in the seventh riding, the carbon nanotubes in the column were not dispersed in the di-ethane, and still retained the bundle structure. In summary, the invention complies with the invention patent , Yuan law proposed patent applications. However, Country continued Page (page is not upside down test Peng, the web page referred to estrogen level) 1246503 described above are merely preferred embodiments of the present invention, for
依本案創作精神所作之等致修 圍内。 '• 厂 ] 發明說明續頁 凡熟悉本案技藝之人士，在援 皆應包含於以下之申請專利範In accordance with the creative spirit of the case, the repairs were made. '• Factory】 Description of the Invention Continued page Anyone who is familiar with the skills of this case should be included in the following patent application.
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