1257433 九、發明說明： 【發明所屬之技術領域】 本發明係關於-種奈麵管陣列結構及其生長方法，尤指—縣用金屬 基底之奈米碳管陣列結構及其生長方法。 【先前技#ί】 奈米碳管係1991年由I i j ima在電麵^電之產物中首次發現之中空碳管， 發表在 1991 年出版的Native 354, 56, Helical Microtubules of Graphitic C^bon。奈米碳管具做之綜合力學性能，如高彈性模量、高揚氏模量與低 岔度，以及髓^電學性能、鮮性能及觸性能。隨著絲碳管螺旋方式 之變化，奈米碳管可呈現出金屬性或半導體性f。因奈米碳管具優異之特性， 其可望於絲電子學、娜醉 '生物學、化學轉辦鱗轉之作用， 而奈米碳管陣列結構因其中奈米碳管排列之整齊有序，使其更利於工業應 用，尤其在場發射顯示及白光燈照明等方面。 、目前形成有序奈米碳管陣列之方法主要係化學氣相沈積法(cyD)。化學氣 相沈積法主要係運用奈米讀之過渡金屬或其氧化物作催化劑，在相對較低 之溫度下熱解含碳之源氣體來製備奈米碳管陣列。 當奈米碳管_顧於場發_对、奸搶、大裤行綠等器件作 為電極時，因場發解面顯示點陣之尋址要求其具良好之轉生，並且能夠 承載較大電流’因此金屬基底對奈米碳管陣列結構仍係最佳城擇。 而目别奈米碳官陣列之生長多以石夕、二氧化石夕、玻璃等為基底 ，而較少 1金屬為基底，這主要係因通常金屬材料會強烈影響化學氣相沈積之生長環 或者因金屬驗催化娜成合金，從而使催化敝去活性，或因為金屬 具催化侧而強烈分贿源氣形成積碳，導致無法正常生長奈米碳管。 μ公開號為CN1241813A之中國專利申請於麵年!月19曰公開一種奈米碳 j組裝結構及-種奈米碳管之組裝方法。該組裝結構包括金屬基底及奈米 ^兩部分，奈米碳管s立於基絲面。該組裝方法係將生長好之單壁夺 ^官分離’純化後製成水轉體；長_存放後，按水溶液不同找高位 ’分選所需長度之奈米碳管原液；然後按所需1勤^入去離子树釋， 用甩膠法或浸入法將絲碳轉餘冑.淨之錢基底表面。 1257433 惟，該組裝方法並未實現於金屬基底上生長奈米碳管陣列，且該法需將 奈米碳管純化、分離、製成水溶膠，還需保存一個月左右，耗時較長，不利 於實際工業生產。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nanotube array structure and a growth method thereof, and more particularly to a carbon nanotube array structure of a metal substrate for a county and a growth method thereof. [Previous technique #ί] The carbon nanotubes were first discovered in 1991 by I ij ima in the product of electric electricity. Published in 1991, Native 354, 56, Helical Microtubules of Graphitic C^bon . The comprehensive mechanical properties of nanocarbon tubes, such as high elastic modulus, high Young's modulus and low twist, as well as the electrical properties, fresh properties and touch properties of the core. The carbon nanotubes may exhibit metallic or semiconducting properties f as the spiral pattern of the carbon nanotubes changes. Because of its excellent properties, the carbon nanotubes are expected to function in silk electronics, biology, and chemical conversion, while the carbon nanotube array structure is neatly arranged in which the carbon nanotubes are arranged. It makes it more suitable for industrial applications, especially in field emission display and white light illumination. At present, the method of forming an ordered carbon nanotube array is mainly a chemical vapor deposition method (cyD). The chemical gas phase deposition method mainly uses a nano-reading 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. When the carbon nanotubes _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 'Therefore the metal substrate is still the best choice for the carbon nanotube array structure. However, the growth of the carbon nano-array array is based on Shi Xi, TiO2, glass, etc., and less than 1 metal is the base, which is mainly due to the fact that the metal material will strongly affect the growth ring of chemical vapor deposition. Or the metal is catalyzed by the metal to catalyze the deuterium activity, or because the metal has a catalytic side and strongly separates the source gas to form carbon deposits, resulting in the inability to properly grow the carbon nanotubes. The Chinese patent application with the publication number CN1241813A is in the face of the year! The company discloses a nano carbon j assembly structure and a method for assembling the carbon nanotubes. The assembled structure comprises a metal substrate and two parts, and the carbon nanotubes s stand on the base surface. The assembly method is to separate the well-grown single-walled separation and purify into a water-converted body; after storage, after long-storage, the high-level solution is selected to sort the required length of the carbon nanotube solution; 1 Diligence into the deionized tree, using silk gelatinization or immersion method to transfer the silk carbon to the ember. The surface of the net money. 1257433 However, the assembly method does not realize the growth of a carbon nanotube array on a metal substrate, and the method requires the carbon nanotube to be purified, separated, and made into a hydrosol, and it needs to be stored for about one month, which takes a long time. Not conducive to actual industrial production.
Ch· Emmenegger 4 人在文獻 Αρρ 1 i ed Surface Sci ence 162-163、 452 456(2000) j Carbon nanotube synthetisized on metallic substrates 中揭示一種於鋁基底上形成奈米碳管陣列之方法。他們於鋁基底上塗覆 ’通過熱處理使Fe(N03)3塗層形成奈米級Fe2〇3顆粒，然後通入碳源 氣乙炔與保護氣體之混合氣體生長奈米碳管陣列。 惟，郷成奈米碳管陣列之過程中為避免金屬基底影響化學氣相沈積之 生f環境’或與催化劑形成合金，或者因其自身具有催化作用而強烈分麟 源氣开滅積碳，該法對金屬基底材料具有很大選擇性，可以生長之金屬材料 只能限制在紹 '鎳等少數材料’從緣制其作為奈絲件更為廣泛之應用: 有雲於此，提供-種對金屬基底讀料無選擇性，於金屬基底上^ 米碳管陣列之方法尤為必要。 - 、不 【發明内容】 本發明目的之一係提供-種適於采用金屬為基底之 本發明之p目的雜供-齡錢級^絲麵管 且該奈米碳管陣列之生長對金屬基底場無特殊竭性。 本發明提供一種奈米碳管陣列結構，其包括一全 石夕層，其厚度至少為9奈米。 秀尤積於金屬基底之 該奈米碳管陣列結構之生長方法包括如下步驟: 首先提供一金屬基底； 該石夕層的厚度至少 該金屬催化劑之厚 然后藉由蒸發方法在金屬基底表面沈積一多 為9奈米； m 接著藉由沈積手段將金屬催化劑沈積於該石夕層表面 度在1奈米及1〇〇奈米之間； 再接著將基底熱處理； 最后通入碳源氣力口熱，長出奈米碳管陣列。 1257433 與先前技術相比，本發明以金屬為基底之奈米碳管陣列結構，因金屬基 底表面與催化劑層之間有一矽過渡層，故，金屬基底與催化劑未直接接觸, 避免金屬基猶奈米碳管生長環境之影響，同時也避Μ额慨劑形成合 金’或者因其自身具有催化作用而強烈分鑛源氣形成積碳，因而實顧4 屬基底上生長奈米碳管_，且·上可於任何_種微電子卫藝所適用之金 屬材料上生長’其生絲態不受影響，在工業顧巾有其實際意義。 :與先前技術相比較，本發g月於金屬基底表面形成一層石夕過渡層，然後於 ^矽過渡層上沈積-層催化劑層生長奈米碳管陣列結構，因其基底為金屬， 從而導電性能更好，能承載較大之電流，適於作為場發射顯示n:電子搶、 大功率行波轉耕之電極；錢奈米碳管_場之金龜底可根據其應 用需要而選擇不同之金屬基底，使碳納米管器件之應用更為廣泛。 w 【實施方式】 、 電極 請參閱第-圖’於金屬基底上生長奈米碳管_之方法包括以下步驟： 步驟1係提供-金屬基底，該金屬基底可用金屬板或形成於基片上之金屬 •般為 步驟2係於金屬基底上沈積一多晶矽層，該矽層厚度至少9夺米， 30至70奈米； 不’、 步驟3係於步驟2形成之多晶碎層上沈積金屬催化劑層，厚度為幾奈米； 步驟4係將步驟3所形成之基底進行熱處理； 步驟5係通入碳源氣與保護氣體之混合氣體，長出奈米碳管陣列。 二圖’錢提供—金屬基紉，可直接翻金屬板或形成料 t上^金屬電極。其中’基片可選用列、石英片、玻璃等材料，但要林 Ιίΐ整度’然後可通過熱蒸鐘、磁控減射、離子束賤射等方法於基片上开 。將選用之金屬板或形成於基片上之金屬電極通過機械拋光、^ 化予拋先4方法使其表面具一定之平整度。 原則上，對於金屬板材料和金屬電極材料之選擇無特殊要求，任何一赛 用之金屬材料㈣於生長奈米碳管陣列，惟，金屬板_ 一屬電極材料於化學氣相沈積之生長溫度下需滿足以下4個條件： 1·不發生溶化； 1257433 2·不與石夕或所用之基片發生共溶· 基片度之溫度範酬，其熱膨脹係數與所用 4·不因吸氫而產生膨脹或碎裂等變化。 其中，對於肖金屬板材料僅需滿足條荆和卿可。 2板材料可選願或不錄鋼等，而電極材料則可選用Ta、沿輪等金 屬’本實施例選用不銹鋼板作為金屬基底。 、 基鍍發等方法於上述金縣底11表面 細二/、子又為成十不米，睛參閱第四圖。然後將金屬催化 電子束洛發沈積、熱沈積或雜法等方法形成於多晶石夕層紅，其 厚度係數奈米至數十奈米均可，其中，金屬催化劑31可為鐵⑽、始(⑸、 鎳㈤或其合金之一，本實施例中選用鐵為催化劑，_厚度為5奈米。 請f閱第’觀積她_之基底魏減巾熱處理，使催 化劑31氧化，熱細化麵麵不同而有制，熱處辦間隨溫度 的增加—少，-般情況熱處理之溫度2GG,t，本實施方式係在綱。⑽ 處理10小時。 … 請參閱第六圖，將上述熱處理後之基底_入一反應舟中，一般係石英 賴舟’紐縣裝入管心英爐之錢室内，在保護氣體下加熱至一預定 溫度，其中，該保護氣體為惰性氣體或氮氣，本實施例選用氮氣，該預定溫 度因催化劑不同而不同，因本實_選職為催侧，—般需加熱到棚一 700 °C，優選溫度為650°c。 再通入如氫氣或氨氣將催化劑還原，使之形成奈米級催化劑顆粒32，通 入碳源氣與保護氣體之混合氣體(此步艮據情況亦可省略），其中碳源氣為 碳氫化合物’可為乙炔、乙烯等，本實施例選用乙炔為碳源氣；該保護氣體 為惰性氣體或氮氣’本實施例選用氬氣，反應5一3〇分鐘，長出奈米碳管陣列 5卜 當然亦可使反應室為真空狀態，只通入碳源氣反應，如乙炔，生長奈米 碳管陣列51。 該奈米碳管陣列51中之奈米碳管排列整齊有序，且生長方向基本垂直於 1257433 金屬j底、適於作為場發射顯示器，電子搶等大功率電子器件之陰極。 明併參閱第七圖至第九圖，第七圖係於石夕基片上用磁控減射方 之Ta電極圖職_ ’第/，細本發卿述之方法於壯騎示之Ta= 圖形上生長所得之奈米碳管_結鄰·#。第九駅細本發明所述方 電子搶德陰極帽上生長所得之奈米碳管陣列結·Μ照片。從圖中可看出、， 以本發明之方法於不同金屬基底上所形成之奈米碳管陣列均整齊有 且均垂直於金屬基底。 1 綜上所述，本創作符合發明專利之要件，爰依法提出專利申請。惟，以 上所述者僅為糊作之雛實施例，軌熟悉本紐藝之人士，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。一 【圖式簡單說明】 第一圖係本發明於金屬基底上生長奈米碳管陣列之方法流程圖。 第二圖係金屬基底之示意圖。 第三圖係沈積有石夕過渡層之金屬基底示意圖。 第四圖係第三圖所示之石夕過渡層上沈積有催化劑之金屬基底示意圖。 第五圖係將第四圖所示之金屬基底熱處理後之示意圖。 第六圖係本發明奈米碳管陣列結構示意圖。 第七圖係於石夕基片上用磁控濺射法形成之鈕(Ta)電極圖形之掃描電鏡照 片（SEM， Scanning Electron Microscope)。 第八圖係以本發明之方法於第七圖所示之Ta電極圖形上生長所得之奈米 碳管陣列之SEM照片。 不、 管陣列之SEM照片。 【主要元件符號說明】 基底 11 矽過渡層 21 催化劑 31 奈米碳管陣列 51 催化劑顆粒 32 第九圖係以本發明之方法於電子搶之鎳(Ni)陰極帽上生長所得之奈米碳A method for forming an array of carbon nanotubes on an aluminum substrate is disclosed in Ch. Emmenegger 4 in the literature Αρρ 1 i ed Surface Science 162-163, 452 456 (2000) j Carbon nanotube synthetisized on metallic substrates. They were coated on an aluminum substrate. The Fe(N03)3 coating was formed into a nano-scale Fe2〇3 particle by heat treatment, and then a carbon nanotube array was grown by a mixed gas of carbon source acetylene and a shielding gas. However, in the process of forming a carbon nanotube array, in order to avoid the influence of the metal substrate on the chemical vapor deposition, or to form an alloy with the catalyst, or because of its own catalytic action, the carbon source is strongly separated from the carbon source. The method has great selectivity for metal base materials, and the metal materials that can be grown can only be limited to a few materials such as s-nickel, which is widely used as a nanowire from the edge: There is no selectivity for metal substrate readings, and the method of carbon nanotube arrays on metal substrates is particularly necessary. - OBJECTS OF THE INVENTION One object of the present invention is to provide a metal-based heterogeneous-age-weight wire surface tube of the present invention and the growth of the carbon nanotube array on a metal substrate There is no speciality in the field. The present invention provides a carbon nanotube array structure comprising a full layer having a thickness of at least 9 nm. The method for growing the carbon nanotube array structure of the metal substrate comprises the following steps: firstly providing a metal substrate; the thickness of the layer is at least the thickness of the metal catalyst and then depositing a surface on the metal substrate by evaporation method Mostly 9 nm; m then depositing a metal catalyst on the surface of the layer by a deposition method between 1 nm and 1 nm; then heat treating the substrate; finally introducing carbon source heat , grow a carbon nanotube array. 1257433 Compared with the prior art, the metal-based carbon nanotube array structure of the invention has a transition layer between the surface of the metal substrate and the catalyst layer, so that the metal substrate and the catalyst are not in direct contact, and the metal base is avoided. The influence of the growth environment of the carbon nanotubes, while also avoiding the formation of alloys by the amount of agent, or the formation of carbon deposits due to its own catalytic action, thus taking into account the growth of carbon nanotubes on the 4th basement _, and · It can be grown on any metal material suitable for microelectronics. The raw silk state is not affected, and it has practical significance in industrial fabrics. Compared with the prior art, the present invention forms a layer of a transition layer on the surface of the metal substrate, and then deposits a layer of catalyst layer on the transition layer to form a carbon nanotube array structure, since the substrate is made of metal, thereby conducting electricity. It has better performance and can carry a large current. It is suitable for field emission display. n: Electron grab, high-power traveling wave conversion tiller; Qiannai carbon tube _ field gold turtle bottom can choose different according to its application needs. Metal substrates make the application of carbon nanotube devices more extensive. w [Embodiment], the electrode please refer to the figure - Figure 'Growing carbon nanotubes on the metal substrate _ The method includes the following steps: Step 1 provides a metal substrate, which can be a metal plate or a metal formed on the substrate • Generally, step 2 is to deposit a polycrystalline germanium layer on the metal substrate, the germanium layer having a thickness of at least 9 m, 30 to 70 nm; and no, step 3 is to deposit a metal catalyst layer on the polycrystalline layer formed in step 2. The thickness is a few nanometers; the step 4 is to heat-treat the substrate formed in the step 3; the step 5 is to pass a mixed gas of the carbon source gas and the shielding gas to grow the carbon nanotube array. The second figure 'money supply' - metal base, can directly turn the metal plate or form the material on the metal electrode. Among them, the substrate can be selected from columns, quartz plates, glass, etc., but it can be opened on the substrate by hot steaming, magnetron reduction, ion beam sputtering, etc. The selected metal plate or the metal electrode formed on the substrate is mechanically polished and polished to a certain degree of flatness. In principle, there is no special requirement for the selection of sheet metal materials and metal electrode materials. Any metal material used in the competition (4) is used in the growth of carbon nanotube arrays. However, the growth temperature of metal sheets _ a group of electrode materials in chemical vapor deposition The following four conditions must be met: 1. No melting occurs; 1257433 2· Does not co-dissolve with Shi Xi or the substrate used · The temperature of the substrate is the temperature, the coefficient of thermal expansion and the 4 used are not due to hydrogen absorption. Changes such as swelling or chipping occur. Among them, for the metal sheet material, only need to meet the Jing and Qing. 2 plate materials may or may not be recorded steel, and the electrode material may be selected from Ta, metal such as wheels. In this embodiment, a stainless steel plate is selected as the metal substrate. The method of base plating and the like is on the surface of the above-mentioned Jinxian bottom 11 and the second is fine. Then, a metal-catalyzed electron beam, a thermal deposition or a hetero-method is formed in the polycrystalline stone layer, and the thickness coefficient thereof is from nanometer to several tens of nanometers, wherein the metal catalyst 31 can be iron (10). ((5), one of nickel (five) or one of its alloys, in this embodiment, iron is used as a catalyst, and the thickness is 5 nm. Please read the heat treatment of the base Wei-Xi towel, which is oxidized, and the catalyst 31 is oxidized. The surface is different and has a system, and the heat is increased with the temperature. The temperature of the heat treatment is 2GG, t. This embodiment is in the scheme. (10) Treatment for 10 hours. ... Please refer to the sixth figure. After the heat treatment, the substrate is inserted into a reaction boat, generally quartz quartz slag 'New County is loaded into the money chamber of the tube heart furnace, and heated under a protective gas to a predetermined temperature, wherein the shielding gas is inert gas or nitrogen gas. In this embodiment, nitrogen gas is selected, and the predetermined temperature is different depending on the catalyst, because the actual _ is selected as the urging side, and generally needs to be heated to a shed of 700 ° C, preferably at a temperature of 650 ° C. Re-injection such as hydrogen or ammonia Gas reduces the catalyst to form a nanoscale catalyst The particles 32 are mixed with a mixture of a carbon source gas and a shielding gas (this step may be omitted according to circumstances), wherein the carbon source gas is a hydrocarbon, which may be acetylene, ethylene, etc., in this embodiment, acetylene is used as a carbon source gas. The protective gas is inert gas or nitrogen. In this embodiment, argon gas is selected, and the reaction is carried out for 5 to 3 minutes, and the carbon nanotube array 5 is grown. Of course, the reaction chamber can be in a vacuum state, and only the carbon source gas is reacted. , such as acetylene, growing carbon nanotube array 51. The carbon nanotubes in the carbon nanotube array 51 are arranged neatly and orderly, and the growth direction is substantially perpendicular to the 1257343 metal bottom, suitable for field emission display, electronic grab The cathode of high-power electronic devices. See also the seventh to ninth figures. The seventh picture is the Ta electrode diagram of the magnetron reduction on the Shi Xiji film. _ '第/, 细本发卿The method is a nano carbon tube obtained by growing on the Ta= pattern of Zhuangqi. _ 邻 · # # 。 。 。 。 。 。 。 。 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈As can be seen from the figure, the method of the present invention is applied to different metal bases. The array of carbon nanotubes formed on the substrate is neat and perpendicular to the metal substrate. 1 In summary, the creation meets the requirements of the invention patent, and the patent application is filed according to law. However, the above is only for the paste. In the case of the younger embodiment, the equivalent modifications or changes made by the person familiar with this New Art in the spirit of the invention should be included in the scope of the following patent application. [The following is a brief description] A flow chart of a method for growing a carbon nanotube array on a metal substrate. The second figure is a schematic diagram of a metal substrate. The third figure is a schematic diagram of a metal substrate deposited with a Shiyue transition layer. The fourth figure is a stone shown in the third figure. Schematic diagram of a metal substrate on which a catalyst is deposited on the transition layer. Fig. 5 is a schematic view showing the heat treatment of the metal substrate shown in Fig. 4. Fig. 6 is a schematic view showing the structure of the carbon nanotube array of the present invention. Scanning Electron Microscope (SEM) of a button (Ta) electrode pattern formed by magnetron sputtering on a substrate. Fig. 8 is a SEM photograph of the obtained carbon nanotube array grown on the Ta electrode pattern shown in Fig. 7 by the method of the present invention. No, SEM photo of the tube array. [Major component symbol description] Substrate 11 矽 Transition layer 21 Catalyst 31 Carbon nanotube array 51 Catalyst particles 32 The ninth figure is the nano carbon grown on the electron-collected nickel (Ni) cathode cap by the method of the present invention.