200906711 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的製備方法， 涉及一種高密度奈米碳管陣列的製備方法。 【先前技術】 尤其 奈米碳管為九十年代初才發現的—種新 奈米材料。奈米碳管的特殊結構決定了其具有特殊的 性質，如高抗張強度和高熱穩定性；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 4。由於奈米碳管具有理想的—維結構及於力學、帝 學、熱學等領域優良的性質，其於材料科學、化⑨ 物理學等交又學科領域已展現出廣闊的應用前景，於 科學㈣以及產業應用上也受到越來越多的關注。、 先珂比較成熟的製備奈米碳管的方法主要包括 電^瓜放電法（Are dlseharge)、錯射燒#法旧咐 及化學氣相沈積法 =7咖，CVD)。其中，化學氣相沈積法和前兩種 获^具有產m控性強、與先前的積體電路 等優點’利於工業上進行大規模合成，因此 近成年備党關注。 細相，採用CVD方法製備奈米碳管陣列的技術已 熟’然直接生長得到的奈米碳管陣列受⑽ 方法生長的限制，於其陣列中奈米碳管的密度基本上 200906711 為確定的，無法任意調控。此外，該方法直接生長的 奈米碳管陣列中奈米碳管的密度在微觀上看為較為 鬆散的，奈米碳管之間的間距大於奈米碳管自身直徑 的數倍’所製備的奈米碳管陣列的密度最大也只於 102克每立方厘米（g/cm3)量級上。因此CVD方法直接 生長得到的奈米碳管陣列中奈米碳管的密度較低。這 種密度較低的奈米碳管陣列於電子、導熱等方面的性 質還不能達到比較理想的要求。200906711 IX. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a carbon nanotube array, and to a method for preparing a high-density carbon nanotube array. [Prior Art] In particular, carbon nanotubes were discovered in the early 1990s as a new nanomaterial. The special structure of the carbon nanotubes determines its special properties, such as high tensile strength and high thermal stability. The carbon nanotubes can exhibit metallic or semiconducting properties as the nanocarbon tube spirals. Because the carbon nanotubes have ideal-dimensional structure and excellent properties in the fields of mechanics, emperor, and heat, they have shown broad application prospects in the fields of materials science, physics, physics, etc., in science (4) And industrial applications are also receiving more and more attention. First, the more mature methods for preparing carbon nanotubes mainly include electric discharge method (Are dlseharge), misfired #法旧咐 and chemical vapor deposition method = 7 coffee, CVD). Among them, the chemical vapor deposition method and the first two have the advantages of strong m-control and previous integrated circuits, which are favorable for large-scale synthesis in the industry. The fine phase, the technique of preparing the carbon nanotube array by CVD method has been cooked. The direct growth of the carbon nanotube array is limited by the growth of the (10) method, and the density of the carbon nanotubes in the array is basically determined by 200906711. Can not be arbitrarily regulated. In addition, the density of the carbon nanotubes in the carbon nanotube array directly grown by the method is relatively loose at a microscopic level, and the spacing between the carbon nanotubes is greater than several times the diameter of the carbon nanotube itself. The density of the carbon nanotube array is also on the order of 102 grams per cubic centimeter (g/cm3). Therefore, the density of the carbon nanotubes in the carbon nanotube array directly grown by the CVD method is low. The low-density carbon nanotube arrays do not meet the ideal requirements for electrical and thermal conductivity.
Don N. Futaba 荨（凊參見 “shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as supercapacitor electrodes" , Don N. Futaba et al.,Don N. Futaba 荨 (凊 “shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as supercapacitor electrodes", Don N. Futaba et al.,
Nature Materials，v〇l 5，P987(2006))利用收縮效 應把單壁奈米碳管收縮成高密度奈米碳管陣列，且證 貫了其所製備的高密度單壁奈米碳管陣列，具有單個 奈米碳管的固有特性，例如大的比表面積、優異的柔 韌性以及導電性等。高密度單壁奈米碳管陣列可應用 於彈性加熱器和密閉能量記憶體件的超級電容器的 电極上，然，該方法製備的工序較複雜。 有鑒於此，提供一種簡單易行的製備高密度、均 勻地疋向排列的奈米碳管陣列的製備方法實為必要。 【發明内容】 一種高密度奈米碳管陣列製備方法，包括：提供 200906711 *幵V成於一基底的奈米碳管陣列；提供一高彈性薄 t均勻拉伸上述的高彈性薄膜後，附着在上述奈米 厌B陣列上，同時對該高彈性薄膜均勻地施加壓力； 保嶋並收縮高彈性薄膜，撤去壓純，分離奈米 碳管陣列與高彈性薄膜’從而得到高密度奈米碳管陣 列。 #與先前技術相比，本發明所提供的高密度奈米碳 官陣列的製備方法具有以下優點：其―，所述的製備 方法簡單易行，有利於用於實際生產；其二，所製備 的的高密度奈米碳管陣列中的奈米碳管均勾地定向 排列，其讀可根據需要控㈣aD方法直接生長所 得到的奈米碳管陣列密度的5〜5〇倍。由於該奈米碳 管陣列在電、熱等方㈣有較好的特性，可以廣泛地 應用在催化電極、電池電極、電磁遮罩、導電材料、 導熱材料、發光材料以及複合㈣等方面。 【實施方式】 以下將結合附圖詳細說明本實施例高密度奈米 碳管陣列的製備方法。 ' 請參閱圖1及圖2,本實施例高密度奈米碳 列20的製備方法主要包括以下步驟： 步驟一：提供—形成於—基底的奈米碳管陣列 20 ’優選地，該陣列為超順排奈米破管陣列。 本貫施例中，奈米碳管陣列2〇的製備方法採用 200906711 化學氣相沈積法，其具體步驟包括：（a)提供一平整 基底’§亥基底可選用p型或N型石夕基底，或選用形成 有氧化層的矽基底，本實施例優選為採用4英寸的矽 基底’（b )在基底表面均勻形成一催化劑層，該催化 劑層材料可選用鐵（Fe)、鈷（Co)、鎳（Nl)或其任 思組合的合金之一；（c)將上述形成有催化劑層的基 底在700〜900°C的空氣中退火約30分鐘〜9〇分鐘； (d)將處理過的基底置於低壓反應爐中，大氣壓強 約〇. 2托（Torr)，在保護氣體環境下加熱到7〇5t：，. 然後通入碳源氣體反應約2〇分鐘，生長得到奈米碳 官陣列。該奈米碳管陣列為多個彼此平行且垂直於基 底生長的奈米碳管形成的純奈米碳管陣列，由於生成 的奈米碳管長度較長，部分奈米碳管會相互纏繞。通 過控制上述生長條件’該超襲奈米碳管陣列中美本 :含有，質’如無定型碳或殘留的催化劑金屬：粒 :、°本貫施例中碳源氣可選用乙炔等化學性質較活带 的碳氫化合物，保護氣體―氣、氨氣或惰料 體。可以理解，本實施例提供的奈米碳管陣列不限於 =備Γ’所述的奈米碳管陣列包括單壁奈米碳 ^車列、雙壁奈米料陣列或多壁以碳管陣列中的 種〇 步驟二：提供-高彈性薄膜30。 聚：的30材料可為高彈性的高分子 口物中的種，如石夕橡膠、順丁橡膠、天然橡膠、 200906711 異戊橡膠或丁苯橡膠。本實施例中採用的高彈性薄膜 3 0為梦橡膠薄膜。 步私一.均勻拉伸上述的高彈性薄膜別後，將 拉伸後的高彈性薄膜3G附着在上述奈米碳管陣列2〇 上’同時㈣高彈性薄膜3G均勻地施加壓力。 其中，均勻拉伸上述的高彈性薄膜3〇為一維拉 伸或者一、准拉伸’一維拉伸為在高彈性薄㈣的長 度或寬度方向上拉伸。二維拉伸為在高彈性薄膜3〇 的長度和寬度兩個方向上同時拉伸。 本κ %例中知用二維拉伸高彈性薄膜。將高彈 性薄膜30進行二維拉伸後，直接將拉伸後的高彈性 薄膜3〇附着在奈米碳管陣列2〇上，具體地，將拉伸 後的南彈性_ 3〇附着在奈米碳管陣㈣遠離基底 的一端’同時對該高彈性薄m 3〇均勾地施加壓力， 以增力:高彈性薄膜30和奈米碳管陣列20之間的附着 力把加于上边的面彈性薄Μ 3〇的表面的壓力的方 σ為垂直於基纟1G方向。上述的施加壓力的大小不 限’可根據實際需要進行選擇，只需保證對高彈性薄 膜30均勻地施加壓力。 /步驟四：保持壓力並收縮高彈性薄膜別，撤去壓 /曰隻上刀離奈米石反官陣列2Q和高彈性薄膜30，從而 付到局雄、度奈米碳管陣列4〇。 彈性薄膜3G時’奈米碳管陣列20隨著高 '寻犋30 一起均勻收縮，由於高彈性薄膜30和奈 200906711 ==陣列20之間的附着力大於奈米碳管陣列20和 :氏10的附看力，隨著高彈性薄膜 碳管陣列2〇從基底J0上脫離文^不/卡 碳管陣列2〇與高雜絲力後，將奈米 奈米竣管陣列40。 刀離，從而得到高密度 膜中去收^问彈性缚膜30為一維收縮高彈性薄 膜3〇或者二維收縮高彈性薄膜3〇。一維收縮高彈性 ，通過在高彈性薄膜的長度或寬度方向上收 :鬲弹性薄膜30。二維收縮高彈性薄膜30為通過在 ㈣㈣膜3G的長度和寬度兩個方向上同時收縮高 祕溥膜30。本實_採用二維收㈣橡膠薄膜。 丄其中，本實施例採用機械法將奈米碳管陣列20 與尚彈性薄膜30分離。即對高彈性薄膜30施加-機 械拉力，直接將高彈性薄膜3〇與奈米碳管陣列別分 離。由於奈米碳管陣㈣中的奈米碳管間的密度高、 結合力強，能夠使得奈米碳管陣列2〇自支撐而不散 開’從而得到高密度奈米碳管_4()。還可採用其他 方法將奈米碳管陣列2G與高彈性薄膜3{)分離。 所製備的高密度奈米碳管陣列40的密度可達到 CVD法直接生長所得到的奈米碳管陣列密度的5 — 倍。 本實施例中獲得的高密度奈米碳管陣列40中的 奈米碳管均句緊密地定向排列，密度為⑽法直接生 長所得的奈米碳管陣列20的15倍。本實施例可通過 12 200906711 . 控制對奈米破管陣列進行的高彈性薄膜3〇收縮程 度的大小’進而控制所述的高密度奈米碳管陣列40 的密度。 本貫施例中咼密度奈米碳管陣列的製備方法具 有以下優點.其-，所述的製備方法簡單易行’有利 於用於貫際生產，其二，所製備的高密度奈米碳管陣 列中的奈米碳管均勻地定向排列，其密度可根據需要 &制為CVD方法直接生長所得到的奈米碳管陣列密度 的5〜50倍。由於該奈米碳管陣列在電、熱等方面都 有較好的特性，可以廣泛地應用在催化電極、電池電 極、電磁遮罩、導電材料、導熱材料、發光材料以及 才旻合材料等方面。 上所述，本發明墙已符合發明專利之要件，遂 依法提出專利申請。惟，以上所述者僅為本發明之較 佳貫施例，自不能以此限制本案之申請專利範圍。舉 凡熟悉本案技藝之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。 【圖式簡單說明】 圖1係本發明實施例高密度奈米碳管陣列的製備 方法的流程示意圖。 圖2係本發明貫施例向後、度奈米碳管陣列的黎】備 過程中奈米碳管陣列隨著高彈性薄膜收縮的形變示 意圖。 13 200906711 【主要元件符號說明】 無 14Nature Materials, v〇l 5, P987 (2006)) shrinks single-walled carbon nanotubes into high-density carbon nanotube arrays using shrinkage effects and demonstrates the high-density single-walled carbon nanotube arrays they have prepared. It has the inherent characteristics of a single carbon nanotube, such as a large specific surface area, excellent flexibility, and electrical conductivity. The high-density single-walled carbon nanotube array can be applied to the electrodes of the elastic heater and the supercapacitor of the closed energy memory device. However, the preparation process of the method is complicated. In view of this, it is necessary to provide a simple and easy method for preparing a high-density, uniformly aligned carbon nanotube array. SUMMARY OF THE INVENTION A method for preparing a high-density carbon nanotube array includes: providing a carbon nanotube array of 200906711*幵V into a substrate; providing a high elastic thinness t to uniformly stretch the above-mentioned high elastic film, and attaching On the above nano-B array, the pressure is uniformly applied to the high elastic film at the same time; the high elastic film is preserved and shrunk, the pure film is removed, and the carbon nanotube array and the high elastic film are separated to obtain high density nano carbon. Tube array. Compared with the prior art, the preparation method of the high-density carbon carbon array provided by the invention has the following advantages: the preparation method is simple and easy to be used, and is beneficial for actual production; The carbon nanotubes in the high-density carbon nanotube array are aligned and aligned, and the reading can be performed 5 to 5 times the density of the obtained carbon nanotube array directly according to the (d) aD method. Since the carbon nanotube array has good characteristics in electric, thermal, etc. (4), it can be widely applied to catalytic electrodes, battery electrodes, electromagnetic masks, conductive materials, heat conductive materials, luminescent materials, and composites (4). [Embodiment] Hereinafter, a method of preparing a high-density carbon nanotube array of this embodiment will be described in detail with reference to the accompanying drawings. Referring to FIG. 1 and FIG. 2, the preparation method of the high-density nanocarbon column 20 of the present embodiment mainly comprises the following steps: Step 1: providing a carbon nanotube array 20' formed on the substrate. Preferably, the array is Super-shunning nano tube breaking array. In the present embodiment, the preparation method of the carbon nanotube array 2〇 adopts the 200906711 chemical vapor deposition method, and the specific steps thereof include: (a) providing a flat substrate, and the p-type or N-type base substrate can be selected. Or, using a germanium substrate formed with an oxide layer, in this embodiment, a catalyst layer is uniformly formed on the surface of the substrate by using a 4 inch germanium substrate (b), and the catalyst layer material may be iron (Fe) or cobalt (Co). One of the alloys of nickel (Nl) or its combination; (c) annealing the substrate on which the catalyst layer is formed in air at 700 to 900 ° C for about 30 minutes to 9 minutes; (d) The substrate is placed in a low-pressure reactor at a pressure of about 2 Torr, heated to 7 〇 5t in a protective gas atmosphere, and then passed through a carbon source gas for about 2 minutes to grow to obtain nanocarbon. Official array. The carbon nanotube array is a plurality of pure carbon nanotube arrays formed by a plurality of carbon nanotubes which are parallel to each other and which are grown perpendicular to the substrate. Due to the long length of the formed carbon nanotubes, some of the carbon nanotubes are entangled with each other. By controlling the above growth conditions, the super-investigated carbon nanotube array in the US: contains, the quality of, such as amorphous carbon or residual catalyst metal: particles:, the carbon source gas in the present application can be selected from acetylene and other chemical properties More live hydrocarbons, protecting gas - gas, ammonia or inert material. It can be understood that the carbon nanotube array provided by the embodiment is not limited to the carbon nanotube array, and the carbon nanotube array includes a single-walled nano carbon array, a double-walled nano-particle array, or a multi-wall carbon nanotube array. Step 2 of the seeding method: providing a high elastic film 30. Poly: 30 materials can be high-elasticity in the polymer mouth, such as Shixi rubber, butadiene rubber, natural rubber, 200906711 isoprene rubber or styrene-butadiene rubber. The high elastic film 30 used in this embodiment is a dream rubber film. Step 1. After uniformly stretching the above-mentioned high elastic film, the stretched high elastic film 3G is attached to the above-mentioned carbon nanotube array 2' while the (4) high elastic film 3G is uniformly applied with pressure. Among them, the above-mentioned high elastic film 3 均匀 is uniformly stretched or one, and the quasi-stretched 'one-dimensional stretch is stretched in the length or width direction of the high elastic thin (four). The two-dimensional stretching is simultaneous stretching in both the length and width of the high elastic film 3〇. The κ% example is known to use a two-dimensionally stretched high elastic film. After the high elastic film 30 is two-dimensionally stretched, the stretched high elastic film 3〇 is directly attached to the carbon nanotube array 2〇, specifically, the stretched south elastic _3〇 is attached to the nai The carbon carbon tube array (4) is away from the end of the substrate while simultaneously applying pressure to the highly elastic thin m 3 , to increase the force: the adhesion between the high elastic film 30 and the carbon nanotube array 20 is added to the upper side. The square σ of the pressure of the surface of the surface of the elastic sheet is perpendicular to the direction of the base 1G. The above-mentioned application pressure is not limited in size, and can be selected according to actual needs, and it is only necessary to uniformly apply pressure to the highly elastic film 30. /Step 4: Maintain the pressure and shrink the high elastic film. Remove the pressure/曰 and only remove the nanometer stone reverse array 2Q and the high elastic film 30, so as to pay for the male and female carbon nanotube arrays. When the elastic film 3G, the carbon nanotube array 20 uniformly shrinks together with the high 'seek 30, since the adhesion between the high elastic film 30 and the nanometer 200906711 == array 20 is greater than that of the carbon nanotube array 20 and 10 The attached force, with the high elastic film carbon nanotube array 2 脱离 detached from the substrate J0 after the text ^ not / card carbon tube array 2 〇 with high hybrid force, the nano-nano tube array 40. The knife is separated to obtain a high-density film to receive the elastic bond film 30 as a one-dimensional shrinkage high elastic film 3〇 or a two-dimensional shrinkage high elastic film 3〇. The one-dimensional shrinkage is highly elastic, and the elastic film 30 is received by the length or width direction of the high elastic film. The two-dimensionally contracted high elastic film 30 is obtained by simultaneously shrinking the high secret film 30 in both the length and the width of the (four) (iv) film 3G. This is a two-dimensional (four) rubber film. In the present embodiment, the carbon nanotube array 20 is separated from the still elastic film 30 by a mechanical method. That is, a mechanical tension is applied to the highly elastic film 30 to directly separate the high elastic film 3〇 from the carbon nanotube array. Due to the high density and strong bonding between the carbon nanotubes in the carbon nanotube array (4), the carbon nanotube array 2 can be self-supported without being dispersed, thereby obtaining a high-density carbon nanotube_4(). The carbon nanotube array 2G can also be separated from the highly elastic film 3{) by other methods. The density of the prepared high-density carbon nanotube array 40 can be five times as high as the density of the carbon nanotube array obtained by direct growth of the CVD method. The carbon nanotubes in the high-density carbon nanotube array 40 obtained in this example are closely aligned, and the density is 15 times that of the carbon nanotube array 20 obtained by the direct growth of the (10) method. This embodiment can control the density of the high-density carbon nanotube array 40 by controlling the size of the high elastic film 3〇 shrinkage performed on the nano-tube array by 12 200906711. The preparation method of the tantalum density carbon nanotube array in the present embodiment has the following advantages. The preparation method is simple and easy to perform for the continuous production, and secondly, the prepared high density nano carbon The carbon nanotubes in the tube array are uniformly aligned, and the density thereof can be 5 to 50 times the density of the obtained carbon nanotube array directly grown according to the requirements of the CVD method. Since the carbon nanotube array has good characteristics in terms of electricity and heat, it can be widely applied to catalytic electrodes, battery electrodes, electromagnetic masks, conductive materials, heat conductive materials, luminescent materials, and chelating materials. . As mentioned above, the wall of the invention has met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application in this case. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic flow chart showing a method of preparing a high density carbon nanotube array according to an embodiment of the present invention. Fig. 2 is a view showing the deformation of the carbon nanotube array with the contraction of the high elastic film in the backward and the carbon nanotube array in the embodiment of the present invention. 13 200906711 [Explanation of main component symbols] None 14