200946709 ^ 九、發明說明： *【發明所屬之技術領域】 本發明涉及一種奈米材料的備方法，尤其涉及一種奈 米碳管的製備方法。 【先前技術】 奈米碳管（Carbon Nanotube，CNT)係一種新型碳材 料，由日本研究人員Iijima在1991年在電弧放電的產物中 發現，請參見"Helical Microtubules of Graphitic Carbon”，S. 〇 Iijima，Nature，vol.354, p56 (1991)。奈米碳管具有優良的 综合力學性能，如高彈性模量、高楊氏模量和低密度，以 及優異的電學性能、熱學性能和吸附性能。隨著奈米碳管 螺旋方式的變化，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特性，因此可望其在奈米電子學、 材料科學、生物學、化學等領域中發揮重要作用。 目前，製備奈米碳管的方法主要係化學氣相沈積法 (CVD )。化學氣相沈積主要係運用過渡金屬或其氧化物 © 作為催化劑，在相對較低的溫度下分解含碳的源氣體，在 所提供的基底上生長奈米碳管。 當奈米碳管應用於場發射顯示器、電子槍、大功率行 波管等器件時，因為場發射平面顯示點陣的定址要求具有 良好的導電性且能夠承載較大電流的電極；電子槍、大功 率行波管等器件的陰極也需要能承載較大電流的基底，而 對於這些應用，金屬基底為最佳材料。 目前，由於奈米碳管的生長多以過渡金屬為催化劑， 由於這種過渡金屬催化劑易與其他金屬形成合金，從而使 7 200946709 、 催化劑失去活性，導致無法正常生長奈米碳管，因此奈米 . 碳管的生長多採用矽、二氧化矽、玻璃等材料作為基底， 而無法在金屬基底上生長奈米碳管。200946709 ^ IX. Description of the invention: * [Technical field to which the invention pertains] The present invention relates to a method for preparing a nanomaterial, and more particularly to a method for preparing a carbon nanotube. [Prior Art] Carbon Nanotube (CNT) is a new type of carbon material discovered by Japanese researcher Iijima in the arc discharge product in 1991. See "Helical Microtubules of Graphitic Carbon", S. 〇 Iijima, Nature, vol. 354, p56 (1991). Carbon nanotubes have 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. With the change of the helical mode of the carbon nanotubes, the carbon nanotubes can exhibit metallic or semiconducting properties. Due to the excellent properties of the carbon nanotubes, it is expected to be in nanoelectronics, materials science, biology, At present, the method for preparing carbon nanotubes is mainly chemical vapor deposition (CVD). Chemical vapor deposition mainly uses transition metals or their oxides as catalysts, at relatively low The carbon-containing source gas is decomposed at a temperature, and a carbon nanotube is grown on the provided substrate. When the carbon nanotube is applied to a field emission display, an electron gun, a high-power traveling wave tube When the device is used, the field emission plane shows that the addressing of the lattice requires an electrode with good conductivity and can carry a large current; the cathode of the device such as an electron gun and a high-power traveling wave tube also needs a substrate capable of carrying a large current, and For these applications, the metal substrate is the best material. At present, because the growth of the carbon nanotubes is mostly based on the transition metal, the transition metal catalyst is easy to form alloys with other metals, so that the catalyst is inactivated. The carbon nanotubes cannot be grown normally, so the growth of the carbon nanotubes is mostly based on materials such as ruthenium, ruthenium dioxide, and glass, and the carbon nanotubes cannot be grown on the metal substrate.
Ch. Emmenegger揭示了 一種在金屬基底上形成奈米 碳管陣列的方法，請參見“Carbon nanotube synthesized on metallic substrate”， Ch. Emmenegger, Applied Surface Science，vol.162-163, P452-456 (2000)。他們通過在鋁基底 上塗敷上硝酸鐵（Fe(N03)3)，通過熱處理使Fe(N03)3塗 φ 層形成奈米級氧化鐵（Fe203 )顆粒，以奈米級的Fe203顆 粒為催化劑，然後通入乙炔碳源氣與保護氣體的混合氣體 使奈米碳管陣列長出。然，由於Fe203導電性能較差，使 奈米碳管與金屬基底的電性接觸較差，限制了奈米碳管作 為電子器件的應用。且，該方法需要經過熱處理將過渡層 處理為奈米級顆粒催化劑，增加了於金屬基底上生長奈米 碳管的工藝步驟，使成本較高。 有鑑於此，提供一種可在金屬基底上直接生長奈米碳 © 管，無須在金屬基底與奈米碳管之間增加過渡層或催化 劑，工藝簡單，成本較低，適合大量生產的奈米碳管的製 備方法實為必要。 【發明内容】 一種奈米碳管的製備方法，其包括以下步驟：提供一 銅基底，對銅基底的表面進行拋光處理；將拋光處理後 銅基底置於一加熱爐中，通入保護氣體後，加熱至400 °C -800°C ;向加熱爐中通入碳源氣，於400°C -800°C下生 長奈米碳管。 8 200946709 * » 與先前技術相比較，本技術方案所提供的奈米碳管的 .製備方法，可直接在金屬銅上生長奈米碳管，且無須在 金屬銅和奈米碳管之間增加過渡層，工藝簡單，成本較 低，適合大量生產。 【實施方式】 卩下將結合附圖及具體實施例詳細說明本技術方案所 提供的奈米礙管的製備方法。 睛參閱圖1，本技術方案實施例提供一種製備奈米碳 e 管的方法，具體包括以下步驟： 步驟-：提供-銅基底，對銅基底的表面進行抛光處 所述拋光處理的過程包括以下步驟： 的砂紙沿第一方向反復 。而後，除去銅基底表 首先，採用一 600目-800目 摩擦銅基底的表面3分鐘-5分鐘 面因摩擦產生的粉末。 的砂紙沿第二方向反 。而後’除去銅基底 ❹ 其次’採用一 1000目_13〇〇目 復摩擦銅基底的表面5分鐘_8分鐘 表面因摩擦產生的粉末。 復摩2美1500目，〇〇目的砂紙沿第-方向反 復摩擦銅基底的表面1〇分鐘_15分 底表面因摩擦產生㈣末。讀。而後，除去銅基 也一方ί與第二方向之間形成-夾角…“ ，優選地’α490〇ο上述除去 的粉末的方㈣風切方法，可_^^摩擦產生 所述銅基底的具體形狀不限，優選地，所述銅基底為 9 200946709Ch. Emmenegger discloses a method of forming a carbon nanotube array on a metal substrate, see "Carbon nanotube synthesized on metallic substrate", Ch. Emmenegger, Applied Surface Science, vol. 162-163, P452-456 (2000) . They applied ferric nitrate (Fe(N03)3) on the aluminum substrate, and heat-treated Fe(N03)3 to form φ layer to form nano-sized iron oxide (Fe203) particles, and nano-sized Fe203 particles as catalyst. Then, a mixture of acetylene carbon source gas and shielding gas is introduced to grow the carbon nanotube array. However, due to the poor conductivity of Fe203, the electrical contact between the carbon nanotubes and the metal substrate is poor, which limits the application of the carbon nanotubes as an electronic device. Moreover, the method requires heat treatment to treat the transition layer into a nano-sized particle catalyst, which increases the process steps for growing the carbon nanotubes on the metal substrate, resulting in higher cost. In view of this, there is provided a nano carbon tube which can be directly grown on a metal substrate, without adding a transition layer or a catalyst between the metal substrate and the carbon nanotube, and has a simple process and low cost, and is suitable for mass production of nano carbon. The preparation method of the tube is really necessary. SUMMARY OF THE INVENTION A method for preparing a carbon nanotube includes the steps of: providing a copper substrate to polish a surface of the copper substrate; placing the polished copper substrate in a heating furnace, and introducing a protective gas , heating to 400 ° C -800 ° C; into the furnace into the carbon source gas, at 400 ° C -800 ° C growth of carbon nanotubes. 8 200946709 * » Compared with the prior art, the preparation method of the carbon nanotube provided by the technical solution can directly grow the carbon nanotube on the metal copper without adding between the metal copper and the carbon nanotube The transition layer is simple in process and low in cost, and is suitable for mass production. [Embodiment] A method for preparing a nano tube which is provided by the present technical solution will be described in detail with reference to the accompanying drawings and specific embodiments. Referring to FIG. 1 , an embodiment of the present technical solution provides a method for preparing a nano carbon tube, specifically comprising the following steps: Step-: providing a copper substrate, polishing the surface of the copper substrate, the polishing process includes the following Step: The sandpaper is repeated in the first direction. Then, the copper base table was removed. First, a surface of the copper substrate was rubbed with a mesh of 600 mesh to 800 mesh for 3 minutes to 5 minutes. The sandpaper is reversed in the second direction. Then, the copper substrate was removed. Next, a 1000 mesh _13 mesh was used to rub the surface of the copper substrate for 5 minutes to 8 minutes. After rubbing 2 US 1500 mesh, the eye-catching sandpaper repeatedly rubs the surface of the copper base in the first direction for 1 _ 15 minutes. The bottom surface is generated by friction (4). read. Then, the copper base is removed and the angle between the second direction and the second direction is formed. ", preferably 'α490〇ο, the square (4) wind cutting method of the powder removed, the friction can be generated to produce the specific shape of the copper substrate. Not limited, preferably, the copper substrate is 9 200946709
P 長方體狀’該銅基底的厚度為0.5厘米-5厘米，盆用於· • 生長奈米碳管的表面的面積為4平方厘米_1〇〇平方厘米。 上述對銅基底表面進行拋光處理的目的為：其一，使 銅基底表面盡可能平整和光滑’有利於奈米碳管的生 長’其一’在對銅基底表面採用砂紙進行拋光處理的過 程中，由於砂紙係沿不同的方向摩擦銅基底，且砂紙較 細，因此在銅基底的表面會形成細小的網狀劃痕或溝槽。 步驟二：將拋光處理後銅基底置於一反應爐中，通入 0 保護氣體後，加熱至400。(：-800。(：。 將上述拋光處理後的銅基底裝入一反應舟中，該反應 舟一般為石英舟，將反應舟裝入反應爐中，該反應爐可為 箱式加熱爐或管式加熱爐等’本實施例優選為管式加熱 爐，將反應舟置於管式加熱爐中央，通入保護氣體後，加 熱至400°C-800°C溫度，優選地，加熱至7〇〇°c。 在上述加熱過程中’銅基底表面網狀劃痕或溝槽進一 步形成大小均勻的銅顆粒，該銅顆粒為奈米碳管的生長提 ❿供晶核，起到催化劑的作用。該銅顆粒的直徑為丄奈米_1() 奈米，銅顆粒的密度與拋光時砂紙磨擦的次數和摩擦方向 之間的夾角有關，摩擦的次數越多，摩擦方向之間的夾角 越小，銅顆粒的密度越大。 步驟三：向加熱爐中通入反應氣，40(TC-80(rc溫度 下生長奈米碳管一段時間。 向加熱爐中通入碳源氣與保護氣體的混合氣體形成 的反應氣，其中碳源氣為碳氫化合物，可為乙炔、乙烯等， 由於碳源氣在反應過程中首先需要裂解，而乙炔的裂解溫 200946709 ，較低，故本實施例優選乙炔為碳源氣。保護氣體為惰性 ,氣體或氮氣，本實施例優選為氮氣。40(rc _80(rc溫度下， 生長奈米碳管5分鐘-30分鐘。由於銅基底形成有大小均 勻的銅^粒，該銅顆粒在奈米碳管的生長過程為奈米碳管 的生長提供了晶核，即銅顆粒起催化劑的作用，使奈米碳 吕才于以生長。冷卻後，取出銅基底，於銅基底的表面形成 有複數個奈米碳管。 请參閱圖2及圖3，本實施例中所製備的奈米碳管於 ©銅基底的表面無序排列，該奈米碳管的一端與銅基底連 接’ 5亥奈米碳管的直徑為5奈米_2〇奈米。 本技術方案所提供的奈米碳管的製備方法，可直接於 金屬銅上生長奈米碳管，且無須在金屬銅和奈米碳管之 間增加過渡層，工藝簡單，成本較低，適合大量生產。 採用本技術方案的方法可直接於場發射顯示器、電子 搶、大功率行波管等電子器件的電極上形成奈来碳管， 避S 了先製備奈米碳管，再把奈米碳管钻附到 ©器件上的複雜過程。 ^綜上所述，本發明確已符合發明專利之要件，遂依法 提出專利申睛。惟，以上所述者僅為本發明之較佳實施例， 自不能以此限制本案之申請專利範圍。舉凡熟悉本案技藝 =人士援依本發明之精神所作之等效修飾或變化，皆應涵 蓋於以下申請專利範圍内。 11 200946709 « 【圖式簡單說明】 ’ 圖1係本技術方案實施例的奈米碳管的製備 程圖。 及法的流 圖2係本技術方案實施例所製備的奈米碳管的掃描電 鏡照片。 圖3係本技術方案實施例所製備的奈米碳管的透射電 鏡照片。 【主要元件符號說明】 無 ❹ 12P cuboid shape The copper substrate has a thickness of 0.5 cm to 5 cm, and the pot is used for the surface of the growth carbon nanotube to have an area of 4 cm 2 〇〇 1 cm 2 . The above purpose of polishing the surface of the copper substrate is as follows: First, the surface of the copper substrate is as flat and smooth as possible, which is beneficial to the growth of the carbon nanotubes, which is in the process of polishing the surface of the copper substrate with sandpaper. Since the sandpaper rubs the copper substrate in different directions and the sandpaper is fine, fine mesh scratches or grooves are formed on the surface of the copper substrate. Step 2: The polished copper substrate is placed in a reaction furnace, and after passing through a protective gas of 0, it is heated to 400. (:-800. (: The above-mentioned polished copper substrate is placed in a reaction boat, which is generally a quartz boat, and the reaction boat is loaded into a reaction furnace, which may be a box furnace or The tubular heating furnace or the like is preferably a tubular heating furnace, and the reaction boat is placed in the center of the tubular heating furnace, and after passing through the shielding gas, it is heated to a temperature of 400 ° C to 800 ° C, preferably, to 7 〇〇°c. During the above heating process, the mesh scratches or grooves on the surface of the copper substrate further form copper particles of uniform size, which serve as a catalyst for the growth of the carbon nanotubes for the growth of the carbon nanotubes. The diameter of the copper particles is 丄 nanometer_1() nanometer, and the density of the copper particles is related to the angle between the number of rubbing of the sandpaper during polishing and the rubbing direction. The more the number of rubbing, the more the angle between the rubbing directions Small, the higher the density of copper particles. Step 3: Pass the reaction gas into the heating furnace, 40 (TC-80 (the carbon nanotubes are grown at a temperature of rc for a period of time. The carbon source gas and the shielding gas are introduced into the heating furnace). a reaction gas formed by a mixed gas in which a carbon source gas is hydrocarbon The compound may be acetylene, ethylene or the like. Since the carbon source gas first needs to be cracked during the reaction, and the acetylene cracking temperature is lower at 200946709, the acetylene is preferably a carbon source gas in this embodiment. The shielding gas is inert, gas or Nitrogen, this embodiment is preferably nitrogen. 40 (rc _80 (at rc temperature, growing carbon nanotubes for 5 minutes to 30 minutes. Since the copper substrate is formed with uniform size copper particles, the copper particles are in the carbon nanotubes The growth process provides a nucleus for the growth of the carbon nanotubes, that is, the copper particles act as a catalyst, so that the nanocarbon is grown. After cooling, the copper substrate is taken out, and a plurality of nanometers are formed on the surface of the copper substrate. Referring to FIG. 2 and FIG. 3, the carbon nanotubes prepared in this embodiment are disorderly arranged on the surface of the copper substrate, and one end of the carbon nanotube is connected with the copper substrate '5 Heiner carbon tube The diameter of the nanometer is 2 nanometers and 2 nanometers. The preparation method of the carbon nanotubes provided by the technical solution can directly grow the carbon nanotubes on the metal copper, and does not need to be between the metal copper and the carbon nanotubes. Increase the transition layer, the process is simple, the cost is low, suitable Mass production. The method of the technical solution can directly form the carbon nanotubes on the electrodes of the electronic devices such as the field emission display, the electronic grab, and the high-power traveling wave tube, avoiding the preparation of the carbon nanotubes first, and then the nano carbon nanotubes. The complicated process of attaching the carbon tube to the © device. In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is legally claimed. However, the above description is only a preferred embodiment of the present invention. It is not possible to limit the scope of the patent application in this case. Any equivalent modifications or changes made by the person skilled in the art to the spirit of the present invention shall be covered by the following patent application. 11 200946709 « [Simple description 1 is a preparation diagram of a carbon nanotube according to an embodiment of the present technical solution. Flow diagram 2 of the method is a scanning electron micrograph of a carbon nanotube prepared by an embodiment of the present technical solution. Fig. 3 is a transmission electron micrograph of a carbon nanotube prepared by an embodiment of the present technical solution. [Main component symbol description] None ❹ 12