200407260 玖、發明說明 【發明領域】 本發明係關於-種奈米碳管生長方法，尤指—種奈㈣管陣列生長 方法。 、、 【發明背景】 奈米碳管係-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^有五元環 或七元環。奈米碳管係在年由π細在電弧放電的產物中首次讀 =，發表在年出版的Nature 354,56。奈米石炭管之特殊結構決定 /、具有優良的綜合力學性能’如高彈性模量、高揚氏模量與低密度，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 疋方式之變化’奈米碳管可呈現出金屬性或半導體性質。由於奈米 碳管的優異·，因此可望其在奈米f子學、材料科學 等領域中發揮重要作用。 物予化子 風目前製備絲碳管之方法主要有放紐、脈衝f射蒸發法及# :乳目沈積法幾種。電弧放電及雌雷射蒸發法形成之奈米碳管有以下 2個缺點：⑴奈料管產量較低；⑵奈米碳管與其他奈麵粒混雜， ^成t碳管的純度很低’還需要複雜之淨化工藝，增加製造成本；⑶ 只人B之生長方向無法控制，所形成之奈米碳管無序混亂，難於工業 。娜财序奈麵管陣_方法目社要魏學齡沈積法1、 子乳相沈積主要係運用奈米尺度的過渡金屬或其氧化物作為催化劑， 在相對低的溫度下熱解含叙源氣體來製備奈米碳管陣列。 6200407260 (1) Description of the invention [Field of the invention] The present invention relates to a method for growing carbon nanotubes, and more particularly to a method for growing nanotube arrays. [Background of the invention] Nano carbon tube system-a kind of hollow tube made of carbon atoms with a diameter of the order of nanometers. It is a six-membered ring in the central part of the graphite layer of the nano carbon tube, and at the end or turning part ^ There are five or seven membered rings. The carbon nanotube system was first read in the products of arc discharge by π, published in Nature 354,56. The special structure of the nanometer carbon tube determines that it has excellent comprehensive mechanical properties such as high elastic modulus, high Young's modulus and low density, as well as excellent electrical, thermal and adsorption properties. Along with the change in the length and diameter of the carbon nanotube, the carbon nanotube can exhibit metallic or semiconductor properties. Due to the superiority of nanometer carbon tubes, it is expected to play an important role in the fields of nanometers and materials science. The physical method of preparing the carbon fiber is currently the main methods of preparing carbon fiber tubes are radio button, pulse f-evaporation method and #: milk mesh deposition method. The carbon nanotubes formed by the arc discharge and female laser evaporation methods have the following two disadvantages: the output of the carbon nanotubes is low; the carbon nanotubes are mixed with other carbon particles, and the purity of the carbon tubes is very low. A complicated purification process is also needed to increase the manufacturing cost; ⑶ The growth direction of person B cannot be controlled, and the formed carbon nanotubes are disordered and chaotic, which is difficult for industry. Nacai sequence noodle tube array_Method Mushe wants Wei Xueling's deposition method 1. Sub-milk phase deposition mainly uses nano-scale transition metals or its oxides as catalysts to pyrolyze Syrian source gases at relatively low temperatures To prepare an array of carbon nanotubes. 6
發明說明續頁 L 见寸善荨人在文獻 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3〇(rc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70(rc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，有序奈米碳管陣歹 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米碳管之外表 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爾力較弱。第八圖係依該方法生長所得之 奈米碳管陣列放人二氯乙烧中超聲侧1Q分鐘後之透射電子顯:鏡 CTEM’ Transmission Electron Microscope)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燒中。 ^ 有鑑於此，提供一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—種奈米碳管陣列生長方法，其生長太 米石屄官陣列中的奈米碳管表面乾淨平滑，通過凡德瓦爾力社卜不 束狀’即為束狀絲碳管陣列。 。。成％、疋的Description of the Invention Continued L See the method of preparation described by Cunshan Xunren in Science 283,512-514 (1999), Self-oriented regular arrays of carbon nanotubes and their field emission properties: First, a porous silicon substrate is provided. The pore diameter is about 3 nanometers, and then a photocatalyst-iron layer with a regular pattern is formed on the substrate by an electron beam evaporation method through a photomask. Anneal, then place the substrate in a quartz reaction boat and send it to the central reaction chamber of the quartz tube reactor. Under the protection of argon, heat the reactor to 70 ° C, and then pass ethylene into the flow at 1000 sccm Gas, react for 15-60 minutes, and then cool the reaction furnace to room temperature. The ordered carbon nanotube array is deposited on the iron-containing area on the substrate, and the carbon nanotube is perpendicular to the substrate. However, the carbon nanotube is perpendicular to the substrate. During the growth process, amorphous carbon will be deposited on the outer surface of the carbon nanotubes at the same time, which will reduce the Van der Waals force between the carbon nanotubes. Van der Waals Weak. The eighth picture is a transmission electron microscope (CTEM 'Transmission Electron Microscope) photo of the carbon nanotube array grown in this method after being placed on the ultrasonic side of dichloroethane for 1Q minutes, which can be seen from the ninth picture After the ultrasonic action, the carbon nanotubes in the carbon nanotube array have been basically dispersed in dichloroethane. ^ In view of this, it is necessary to provide an improved method for growing carbon nanotube arrays. [Objective of the Invention] This The purpose of the invention is to provide a method for growing a carbon nanotube array. The surface of the carbon nanotubes growing in the tamarite eunuch array is clean and smooth. Tube array ... %%
ZUU4U/Z0U 發明說明續頁 本發明奈米碳管陣列生長方法包括以下步驟 預定溫度後通入碳源氣與保護氣體 入 ， #境、4體之此合乳體，並且保持催化劑溫度與 ^皿度之祕G c以上，碳源氣之分觀細，使奈米碳管陣列從 基底長出。該生長出之奈米碳管_為綠奈米碳管陣列。 【較佳實施例】 請參閱第一圖’本發明之生長方法包括以下步驟：首先提供-平# 基底’於其故㈣化劑，紐進行_理，預加祕絲通入混合氣 體長出奈米碳管陣列。 凊-併茶閱第二圖與第三圖，首先提供一平滑基底1〇，可選用p型或 N型或本質碎晶片或表面有一層氧化秒的發晶片為基底，本發明中選用p 型石夕晶片或表面有-層氧化石夕的石夕晶片作為基底1〇，其為圓形，直徑為 5· 08屋米’厚350微米，將該基底1〇拋光獲得平滑基底。將金屬催化劑卻 细包子束*發沈積、熱沈積錢射法等方法形成於絲底上，其厚f 為幾奈米到幾百奈米，其中金屬催化劑20可為鐵(Fe)、銘(C〇)、鎳(Ni) 或其σ金之一，本實施例選用鐵為催化劑20，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300-4〇〇°c之溫度條件下熱 處理約10小時，使催化劑氧化成顆粒，然後再將其用氫氣或氨氣還原形 成奈米級顆粒，再將處理後的基底切割成矩形基底10。ZUU4U / Z0U Description of the Invention Continued The nano carbon tube array growth method of the present invention includes the following steps: passing in a carbon source gas and a protective gas at a predetermined temperature, and maintaining the temperature of the catalyst and the catalyst. The secret of the degree is above G c, and the carbon source gas has a fine separation, so that the carbon nanotube array grows from the substrate. The grown carbon nanotubes are green carbon nanotube arrays. [Preferred embodiment] Please refer to the first figure, "the growth method of the present invention includes the following steps: firstly provide-flat # substrate" to its caustic agent, perform processing, pre-adding a secret wire to the mixed gas to grow Nano carbon tube array.凊 -Tea read the second and third pictures, first provide a smooth base 10, p-type or N-type or essentially broken wafer or a wafer with a layer of oxidation seconds on the surface can be used as the substrate, p-type is used in the present invention The Shi Xi wafer or Shi Xi wafer with a layer of oxidized Shi Xi on the surface is used as the substrate 10, which is circular and has a diameter of 5.08 m and a thickness of 350 micrometers. The substrate 10 is polished to obtain a smooth substrate. The metal catalyst is formed on the silk bottom with a method of thin bun bundles, hair deposition, thermal deposition, and the like. The thickness f is several nanometers to several hundred nanometers. The metal catalyst 20 may be iron (Fe), Ming ( Co), nickel (Ni), or one of sigma gold. In this embodiment, iron is used as the catalyst 20, and the deposition thickness is 5 nm. The substrate 10 on which the catalyst 20 is deposited is heat-treated in the air at a temperature of 300 to 400 ° C for about 10 hours to oxidize the catalyst into particles, and then reduce it to hydrogen to form a nanometer level with hydrogen or ammonia gas. Granules, and the processed substrate is cut into a rectangular substrate 10.
【發明特徵】 提供一平滑基底，將 催化劑沈積於該基底上 ’將沈積有伽_基底在氣體保 護下加熱至一 將其中一片矩形基底10裝入一反應舟中，一般為石英反應舟，將反 應舟裝入管狀石英爐中央的反應室裏，在氣體保護下加熱至一預定溫 8 發明說明續頁丨 度’其中’該保護氣體為惰性氣體或氬氣，本實施例選用氬氣，該預定 狐1、催化J有關’㈣用鐵為催化劑’則—般加熱獅㈣代，優選 為650°C。 通入碳源氣與保護氣體的混合氣體，其中碳源氣為碳氣化合物，可 為乙炔、乙本實補選用乙块；該保觀體為無氣體或氮氣， 本實施例顧氬氣。通過控制碳源氣的流速來控·化_局部溫度 Tc ’環境溫度直接通過控制石·溫虹來，使催化劑的溫度L與反 應爐中環境溫度TL形成-溫差Μ至少在5(rc以上，控制碳源氣與保護# 體的流量比，使碳職之分壓至少在2_下，優選為分壓在雇以下， 反應5-3G分鐘使奈米碳管陣·從基底上出，如第四騎示，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 及越大’奈米碳官生長雜；而無定型碳的沈積速度與麵氣分壓成正 比，破源氣分壓越低，無㈣碳的沈積速度越慢。故，本發明通過控制 催化劑的溫度1與環境溫度Tl的溫差ΔΤ至少在5(TC以上，使奈米碳管白$ 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，又因 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管 更緊密，故，奈米碳管易於因凡德瓦爾力而聚集形成束狀，其透射電子 顯微鏡照片請參閱第六圖所示。 故，採用本發明之方法製備的奈米碳管陣列為束狀奈米碳管陣列， 9 200407260[Features of the invention] A smooth substrate is provided, and the catalyst is deposited on the substrate. 'The deposited substrate is heated under the protection of a gas until a rectangular substrate 10 is loaded into a reaction boat, generally a quartz reaction boat. The reaction boat is installed in the reaction chamber in the center of the tubular quartz furnace, and heated to a predetermined temperature under the protection of gas. 8 Description of the invention continued on the following page: Wherein, the protective gas is an inert gas or argon. In this embodiment, argon is used. It is planned that the fox 1, catalysis J is related to the use of iron as a catalyst, and the griffon generation is generally heated, preferably 650 ° C. A mixed gas of a carbon source gas and a protective gas is passed in, wherein the carbon source gas is a carbon gas compound, and acetylene and ethyl acetate can be used as a supplementary block; the body is no gas or nitrogen, and argon is considered in this embodiment. By controlling the flow rate of the carbon source gas, the local temperature Tc 'environment temperature is directly controlled by the stone Wenhong, so that the temperature L of the catalyst and the ambient temperature TL in the reactor are formed-the temperature difference M is at least 5 (rc, Control the flow ratio of the carbon source gas and the protection body, so that the partial pressure of the carbon is at least 2_, preferably the partial pressure is below the employment, and the nano-carbon array will emerge from the substrate in 5-3G minutes, such as The fourth riding show, and its scanning electron microscope photograph, please refer to the fifth figure. Because the growth rate of carbon nanotubes is proportional to the temperature difference between the catalyst temperature and the ambient temperature, the greater the temperature, the more carbon nanotubes grow; The deposition rate is proportional to the surface gas partial pressure. The lower the source gas partial pressure, the slower the deposition rate of thorium-free carbon. Therefore, the present invention controls the temperature difference ΔT of the catalyst temperature 1 and the ambient temperature T1 to be at least 5 (TC Above, the growth rate of carbon nanotubes is increased; by adjusting the flow ratio of the carbon source gas to the mixed gas, the carbon source gas fractional pressure is at least 20% or less, and the deposition rate of amorphous carbon is slowed down. Using this process The carbon nanotubes grown after the condition are dry The smooth surface and the Van der Waals force between the carbon nanotubes are relatively large, and because the substrate is a smooth substrate, the grown carbon nanotubes are closer than the carbon nanotubes grown on a porous substrate. Rice carbon tubes are easy to gather into a bundle shape due to van der Waals force, and the transmission electron microscope photos are shown in Figure 6. Therefore, the nano carbon tube array prepared by the method of the present invention is a bundled nano carbon tube array. , 9 200407260
I發明說明續頁I 且該束狀結構嫩，糾恢枝 乳乙财超耸作謂分鐘，拍得葡㈣，如第七騎示，該陣财的夺 米碳管沒有分散在二氯乙燒中，仍然保持束狀結構。 不 以上所述者僅為本發明之較佳實施例，舉凡熟悉本案技藝之人士，在援 依本案創作精神所作之等效修飾或變化，皆應包含於以下之申請專利範 圍内。 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，I Description of the Invention Continued page I And the bundle-like structure is tender, and the corrective branch of the milk is superb, and it was photographed in Portuguese. As shown in the seventh riding, the rice-receiving carbon tube of the array of wealth is not dispersed in dichloroethane. During burning, the bundle-like structure is still maintained. The above is only a preferred embodiment of the present invention. For example, those who are familiar with the skills of this case, and equivalent modifications or changes made in accordance with the creative spirit of this case, should be included in the scope of patent application below. In summary, the present invention complies with the elements of the invention patent, and the patent application is filed according to law. but,
□續次頁（發明說明頁不敷使用時，請註記並使用續頁)□ Continued pages (If the description page of the invention is insufficient, please note and use the continued pages)