201132583 [0001] [0002]201132583 [0001] [0002]
G 發明說明： 【發明所屬之技術領域】 本發明涉及一種奈米碳營陣列結構及其製備方 [先前技術] 奈米碳管係一種新型之一維奈米材料， ★具有優自$ p 合力學性能，如高彈性模量、高楊氏模量和低密产，= 及優異之電學性能、熱學料和賴性能”轉二 管碳原子排列方式之變化’奈米碳管可呈現出金屬 半導體性質。由於奈米碳管之優異特性，可望其於太 電子學、材料科學、生物學、化學等_中發 用。 法 [0003] 〇 目前，傳統之形成奈米碳管陣列之方法主要係化學氣相 沈積法（CVD)。化學氣相沈積法運用沈積於生長基底上之 奈米尺度之過渡金展或其氧化物作為催化劑，於—固定 溫度下熱解碳源氣體來製備奈米碳管陣列。目前化學氣 相沈積法一般選用平面形狀之硬質生長基底，如石夕基底 • :: ；" ：：-； .；；： 。而該平面形狀之:硬質生長基底由於受反應室尺寸之限 制，其面積無法做到很大，從而使得生長於其上之奈米 碳管陣列面積也無法做到很大。 [0004] 范守善等人於2008年1月1日公開之第200801224號台灣 發明專利申請公佈說明書中揭示了一種大面積生長奈米 碳管膜之方法。該方法具體為提供一硬質曲面基底’並 於該基底之外表面上沈積一催化劑層；將該沈積有催化 劑層之基底放置於一反應室内；向該反應室内通入保護 氣體，使該反應室保持一預定氣壓；加熱反應室至一預 099109016 表單编號A0101 第3頁/共27頁 0992016095-0 201132583 [0005] [0006] [0007] [0008] 099109016 定溫度；向反應室内通入碳源氣體，一預定時間後，於 基底上得到一層奈米碳管膜。該硬質曲面基底可為筒狀 、螺旋狀或其他形狀，其比平面狀矽基底具有更大之生 長面積，能夠充分利用反應室内部空間，使得一固定容 量空間之反應室内可容納更大面積之基底，從而實現奈 米碳管膜於較小反應室内之大面積生長。 然而，上述製備方法所採用之曲面基底仍為形狀固定之 硬質材料製成，使得生長於其上之奈米碳管膜之形狀也 隨之固定，相對於平面基底，於形狀複雜之曲面基底上 形成之奈米碳管膜之後續利用存於不便，例如當該基底 為螺旋狀時，生長於螺旋狀基底中心部位之奈米碳管膜 難以利用，故，很大程度上限制了該奈米碳管膜之後續 應用。 【發明内容】 有鑒於此，提供一種易於後續利用且具有較大面積之奈 米碳管陣列結構及其製備方法實為必要。 一種奈米碳管陣列結構，該奈米碳管陣列結構包括：一 财彎曲之面狀柔性基底，該柔性基底具有至少一表面； 及至少一奈米碳管陣列生長於該柔性基底之至少一表面 0 一種奈米碳管陣列結構之製備方法，其包括以下步驟： 提供一反應室及一彎曲成預定形狀之面狀柔性基底，該 柔性基底具有至少一表面，且所述柔性基底之至少一表 面上形成一催化劑層；將該柔性基底設置於該反應室内 ;加熱所述柔性基底至一預定溫度；及向所述反應室内 表單編號A0101 第4頁/共27頁 201132583 通入一碳源氣體，於所述柔性基底之至少一表面生長一 奈米碳管陣列。 [0009] ❹ [0010] [0011] ο [0012] [0013] 099109016 相較於先前技術，由於所述柔性基底可發生 '弯曲，故， 於製備奈米碳管陣列時，該柔性基底可根據反應室内之 空間和自身之面積而適當彎曲成不同之形狀以有效利用 反應室内之空間，從而可生長更大面積之奈米碳管陣列 ’田生長奈米碳管陣列後’所述柔性基底可根據實際應 用之需要被展平成—平面形狀結構或f曲成其他形狀， 易於後、Λ利用’使該奈米碳管陣列結構具有較大之應用 範圍。 ·； - . : .. ' 【實施方式】 以下將結合附圖詳細說明本發明實施例提供之奈米碳管 陣列結構及其製備方法。 明參閱圖1 |發明第—實施例提供—種奈米碳管陣列結 構100，該奈米碳管陣列結構1〇〇包括一耐彎曲之面狀柔 性基底102，該柔性基底102具有至少一表面104，及至 少/奈米碳管陣列110生長於該柔性基底102之至少一表 面 1〇4。 所述柔性基底102之材料為耐高溫、可發生彎曲變形且可 支撐所述奈米碳管陣列1丨〇之材料。 首先，該柔性基底102之材料之耐高溫溫度 ，即熔點大於 奈米瓖官陣列110之生長溫度，優選為大於5⑽。C。且所 述系性基底102為具有較小厚度之面狀或片狀基底，其材 料 < 為金屬片、石英片、妙片或陶以等，所述金屬片 第5頁/共27頁 0992016095-0 表車煸號A0101 201132583 可為鉬片、鈦片、锆片、鈮片、钽片、铪片、鎢片、釩 片或上述幾種材料之任意組合之合金片，或不銹鋼片等 。另，該柔性基底102所具有之至少一表面104優選為一 平滑之表面。 [0014] 其次，所述柔性基底102可具有一固定彈性，於一外力之 作用下可發生彈性彎曲變形，且去除該外力後，所述柔 性基底102又可恢復彎曲之前之形狀。或者，所述柔性基 底102可具有一塑性變形能力，於一外力之作用下可發生 塑性彎曲變形，且去除該外力之後，所述柔性基底102仍 可保持其彎曲之形狀，且於施加另一外力於該彎曲後之 柔性基底102上之後，該彎曲後之柔性基底102仍可恢復 到彎曲之前之形狀且不會發生斷裂。該面狀或片狀之柔 性基底102可被彎曲成各種形狀，如可彎曲成筒形形狀、 螺旋形狀或其他規則或不規則之形狀等。所述筒形形狀 包括外周面封閉之筒形形狀和外周面不封閉之表面具有 一開口之筒形形狀。所述表面具有一開口之筒形形狀係 指於筒形形狀之柔性基底102之筒壁沿軸向具有一長條狀 y 開口，該長條狀開口平行於筒形形狀之軸向，從而形成 一外周面未封閉之筒形形狀之柔性基底102。具體為，若 所述柔性基底102被彎曲成外周面封閉之筒形形狀，則沿 垂直於該筒形形狀柔性基底之軸向之橫截面呈封閉之圓 、橢圓或者圓角多邊形等；若所述柔性基底102被彎曲成 外周面未封閉之筒形形狀，則沿垂直於該筒形形狀柔性 基底之軸向之橫截面呈一未封閉之圓、橢圓或者圓角多 邊形等；若所述柔性基底102被彎曲成螺旋形狀或“Z” 099109016 表單編號A0101 第6頁/共27頁 0992016095-0 201132583 字型形狀，則沿垂直於該螺旋形狀或“z”字型形狀之柔 性基底之轴向之截面呈螺旋線形狀或“z”字型形狀。G Description of the Invention: [Technical Field] The present invention relates to a nano carbon camp array structure and a preparation method thereof [Prior Art] A carbon nanotube system is a novel one of the Venom materials, and has a superior self-pive force Learning properties, such as high modulus of elasticity, high Young's modulus and low density, = and excellent electrical properties, thermal materials and properties. "Changes in the arrangement of carbon nanotubes in the second tube." Carbon nanotubes can exhibit metal Semiconductor properties. Due to the excellent properties of carbon nanotubes, it is expected to be used in electronics, materials science, biology, chemistry, etc. [0003] 〇 Currently, the traditional method of forming carbon nanotube arrays Mainly by chemical vapor deposition (CVD). The chemical vapor deposition method uses a nanoscale transition gold alloy deposited on a growth substrate or its oxide as a catalyst to pyrolyze a carbon source gas at a fixed temperature to prepare a naphthalene. Carbon tube array. At present, chemical vapor deposition generally uses a flat-shaped hard growth substrate, such as Shi Xi base • :: ; "::-;.;;: and the shape of the plane: hard growth substrate due to Due to the size of the reaction chamber, the area cannot be made large, so that the area of the carbon nanotube array grown thereon cannot be made large. [0004] Fan Shoushan et al. published on January 1, 2008. A method for growing a carbon nanotube film over a large area is disclosed in the publication of the Taiwan Patent Application Publication No. 200801224. The method specifically provides a hard curved substrate and deposits a catalyst layer on the outer surface of the substrate; The substrate with the catalyst layer is placed in a reaction chamber; a shielding gas is introduced into the reaction chamber to maintain the reaction chamber at a predetermined pressure; and the reaction chamber is heated to a pre-099109016. Form No. A0101 Page 3 / Total 27 Page 0992016095-0 201132583 [0007] [0007] [0008] [0008] 099109016 set temperature; into the reaction chamber into the carbon source gas, after a predetermined time, a layer of carbon nanotube film is obtained on the substrate. The hard curved surface substrate can be cylindrical , spiral or other shape, which has a larger growth area than the planar crucible base, and can fully utilize the space inside the reaction chamber to make a reaction chamber of a fixed capacity space Accommodating a larger area of the substrate, thereby achieving a large area growth of the carbon nanotube film in a smaller reaction chamber. However, the curved substrate used in the above preparation method is still made of a hard material having a fixed shape so as to be grown thereon. The shape of the carbon nanotube film is also fixed, and the subsequent use of the carbon nanotube film formed on the curved substrate having a complicated shape is inconvenient relative to the planar substrate, for example, when the substrate is spiral, it grows on the spiral The carbon nanotube film at the center of the base is difficult to utilize, so the subsequent application of the carbon nanotube film is largely limited. [Invention] In view of this, it is easy to use and have a large area. The carbon nanotube array structure and its preparation method are really necessary. A carbon nanotube array structure comprising: a curved curved flexible substrate having at least one surface; and at least one carbon nanotube array grown on at least one of the flexible substrates Surface 0 A method for preparing a carbon nanotube array structure, comprising the steps of: providing a reaction chamber and a planar flexible substrate bent into a predetermined shape, the flexible substrate having at least one surface, and at least one of the flexible substrates Forming a catalyst layer on the surface; disposing the flexible substrate in the reaction chamber; heating the flexible substrate to a predetermined temperature; and introducing a carbon source gas into the reaction chamber form number A0101, page 4 / total 27 pages 201132583 And growing an array of carbon nanotubes on at least one surface of the flexible substrate. [0009] [0013] [0013] 099109016 Compared to the prior art, since the flexible substrate can be 'bent, when the carbon nanotube array is prepared, the flexible substrate can be The space in the reaction chamber and the area of the chamber are appropriately curved into different shapes to effectively utilize the space in the reaction chamber, so that a larger area of the carbon nanotube array 'field growth carbon nanotube array' can be grown after the flexible substrate can be According to the needs of the actual application, it is flattened into a plane-shaped structure or f-curved into other shapes, which is easy to use, and the use of the carbon nanotube array structure has a large application range. The following is a detailed description of a carbon nanotube array structure and a preparation method thereof according to an embodiment of the present invention with reference to the accompanying drawings. Referring to FIG. 1 , a first embodiment of the invention provides a carbon nanotube array structure 100 comprising a curved flexible substrate 102 having at least one surface. 104, and at least/carbon nanotube array 110 is grown on at least one surface 1〇4 of the flexible substrate 102. The material of the flexible substrate 102 is a material that is resistant to high temperatures, can be bent and deformed, and can support the carbon nanotube array. First, the high temperature resistance of the material of the flexible substrate 102, i.e., the melting point, is greater than the growth temperature of the nano Array 110, preferably greater than 5 (10). C. And the structural substrate 102 is a planar or sheet-like substrate having a small thickness, and the material thereof is a metal piece, a quartz piece, a chip or a ceramic, etc., the metal piece is 5th/total 27 pages 0992016095 -0 The watch number A0101 201132583 may be a molybdenum sheet, a titanium sheet, a zirconium sheet, a tantalum sheet, a tantalum sheet, a tantalum sheet, a tungsten sheet, a vanadium sheet or an alloy sheet of any combination of the above materials, or a stainless steel sheet. Additionally, at least one surface 104 of the flexible substrate 102 is preferably a smooth surface. [0014] Secondly, the flexible substrate 102 can have a fixed elasticity, and elastic bending deformation can occur under the action of an external force, and after the external force is removed, the flexible substrate 102 can restore the shape before bending. Alternatively, the flexible substrate 102 may have a plastic deformation capability, plastic bending deformation may occur under the action of an external force, and after the external force is removed, the flexible substrate 102 may still maintain its curved shape and apply another After the external force is applied to the curved flexible substrate 102, the curved flexible substrate 102 can still return to the shape before bending without breaking. The planar or sheet-like flexible substrate 102 can be bent into various shapes such as a cylindrical shape, a spiral shape, or other regular or irregular shape. The cylindrical shape includes a cylindrical shape in which the outer peripheral surface is closed and a cylindrical shape in which the outer peripheral surface is not closed. The cylindrical shape of the surface having an opening means that the cylindrical wall of the cylindrical flexible substrate 102 has an elongated y opening in the axial direction, and the elongated opening is parallel to the axial direction of the cylindrical shape, thereby forming A flexible substrate 102 having an outer peripheral surface that is not closed in a cylindrical shape. Specifically, if the flexible substrate 102 is bent into a cylindrical shape in which the outer peripheral surface is closed, a circular, elliptical or rounded polygon such as a closed cross section perpendicular to the axial direction of the cylindrically shaped flexible substrate; The flexible substrate 102 is bent into a cylindrical shape in which the outer peripheral surface is not closed, and an unclosed circle, ellipse or rounded polygon or the like is formed along a cross section perpendicular to the axial direction of the cylindrically shaped flexible substrate; The substrate 102 is bent into a spiral shape or "Z" 099109016 Form No. A0101 Page 6 / Total 27 Page 0992016095-0 201132583 The shape of the font is along the axial direction of the flexible substrate perpendicular to the spiral shape or the "z" shape. The cross section has a spiral shape or a "z" shape.
[0015] 再其次，該柔性基底102之厚度以可使該柔性基底102發 生彎曲變形且不發生斷裂為基準，且其厚度越小，該柔 性基底102可產生越大之彎曲變形。如若所述柔性基底 102為金屬片，則該柔性基底102之厚度可為小於等於3毫 米大於等於0. 005毫米，若所述柔性基底102為矽片、石 英片和陶瓷片，則該柔性基底102之厚度可小於等於〇. 3 毫米，優選為小於等於〇. 1毫米並大於等於1微米。本實 施例中，該柔性基底102之材料為0.1¾米之金屬片。 [〇〇16] 該奈米碳管陣列110包括複數奈米碳管，該複數奈来碳管 可為無序排列或有序地垂直於基底排列〃當該奈米碳管 為無序排列時，該複數奈米碳管可為#曲且相互纏繞之 生長於所述柔性基底102之表面。當該奈米碳管為有序地 垂直於柔性基底102排列時，該複數奈米碳管基本為直線 狀，並且，當所述柔性基底處於展平狀態之後，所述[0015] Next, the thickness of the flexible substrate 102 is based on the fact that the flexible substrate 102 is bent and deformed without being broken, and the smaller the thickness, the greater the bending deformation of the flexible substrate 102. If the flexible substrate 102 is a metal sheet, the thickness of the flexible substrate 102 may be less than or equal to 3 mm and greater than or equal to 0.005 mm. If the flexible substrate 102 is a silicon sheet, a quartz sheet, and a ceramic sheet, the flexible substrate The thickness of 102 may be less than or equal to 〇. 3 mm, preferably less than or equal to 〇. 1 mm and greater than or equal to 1 μm. In this embodiment, the flexible substrate 102 is made of a metal sheet of 0.13⁄4 meters. [〇〇16] The carbon nanotube array 110 includes a plurality of carbon nanotubes, and the plurality of carbon nanotubes may be arranged in a disorderly or orderly manner perpendicular to the substrate. When the carbon nanotubes are disorderly arranged The plurality of carbon nanotubes may be #曲曲and intertwined and grown on the surface of the flexible substrate 102. When the carbon nanotubes are arranged in an orderly manner perpendicular to the flexible substrate 102, the plurality of carbon nanotubes are substantially linear, and after the flexible substrate is in a flattened state,
複數奈米碳管基本相互平行，且沿基本垂直於所述柔性 基底102之平滑表面104之方向生長。所述基本平行係指 該複數奈米碳管中之大部分基本沿同一方向延伸，僅有 少數奈米碳管隨機排列’這些奈米碳管不會對奈米碳管 陣列110中大多數奈米琰管之整體取向排列構成明顯影響 。所述基本垂直孫指所述複數奈米碳管中之大部分奈米 碳管垂直於所述黍性基底102之表面104，僅有少數奈米 碳管並不完全燊真所迷柔性基底102，而為近似垂直，如 大於等於80度小於等於1〇〇度。 099109016 表單編號A0101 第 頁/共27頁 0992016095-0 201132583 [0017] [0018] [0019] 。亥奈米碳官陣列結構1 〇 〇可進一步包括一設置於所述柔性 基底102之至少—表面1〇4上之一催化劑層1〇8，所述奈 米碳管陣列110形成於該催化劑層1〇8。該催化劑層1〇8 之材料可選擇為鐵（Fe)、始（c〇)、錄（Ni)或者該 戎種金屬之氧化物，該催化劑層10 8可採用熱沈積、電子 束沈積、蒸鍍或磁控濺射等方法形成於上述柔性基底1〇2 之至少一表面1〇4。該催化劑層1〇8之厚度可根據實際需 要選擇’優選為1奈米至50奈米。本實施例中，所述催化 劑層10 8之材料為鐵，厚度為5奈米，該催化劑層1 〇 8設置 於所述柔性基底102之一個表面1〇4。 此外，若所述柔性基底1(32為—金屬片，朗述奈米碳管 陣列結構100可進-步包括設置於所述柔性基底1〇2和所 述催化劑層108之間之-阻隔層1〇6，該阻隔層1〇6之材 料可為切、氧切或金屬氧化物等，該阻隔層 106具有較小之厚度，該厚度可小於等於⑽微米。本實 施例中，該阻隔層106之材料為5〇奈米之矽層。 、 由於所《性基底1G2可發生彎命，:故所述奈米碳管陣列 結構100可為-平面形狀結構’也可弯曲成筒形形狀垂 直於轴向之載面具有1口之筒形形狀、螺旋形狀、“z 子型形狀、或者其他規則或不規則之形狀等。本實施 例中，所述奈米碳管_結構刚被料成—筒形形狀。 由於該奈米碳管陣列結構1QG具有一柔性基底⑽，故， 該奈米碳管陣列結構1〇〇可根據實際應用之需要而發生彎 曲變形，從而擴大了該奈米碳管陣列結構1〇〇之使用範圍 〇 099109016 表單編號A0101 第8頁/共27頁 0992016095-0 201132583 [〇〇2〇]吻參閱圖2和圖3 ,本發明提供一種上述第一實施例奈米 碳笞陣列結構1 〇 〇之製備方法，其包括以下步驟： [0021] 步驟一，提供一反應室12〇及一彎曲成預定形狀之面狀柔 性基底102，該柔性基底丨〇2具有至少一表面1〇4，且所 述柔性基底1〇2之至少一表面1〇4上形成有一催化劑層 108 ; [0022] 步驟二’將該形成有催化劑層108之柔性基底1〇2設置於 該反應室120内； 〇 [0023] 步驟三，加熱所述柔拄基底1〇2至一預定瀑度； [0024] 步驟四’向所述反應室120内通入一碳源氣體，於所述柔 性基底102形成有催化劑層1Q8之至少一表面生長一奈米 碳管陣列110。 [0025] 以下將對上述各步驟進行詳細說明。 [0026] 於步驟一中，該反應室120可為先前技術中之CVD反應室 0 。本實施例中，該反應室120為一用於CVD反應之石英管 式加熱爐。該反應室120包括分別設置於該反應室120兩 端之一進氣口 122及一出氣口 124，該進氣口 122及出氣 口 124位於該石英管式加熱爐沿軸向之兩端。該柔性基底 102之至少一表面104優選為一平滑表面’該平滑表面可 通過機械拋光或電化學拋光等方法獲得° [0027] 所述催化劑層108可採用熱沈積、電子束沈積、落錢或磁 控濺射等方法形成於上述柔性基底102之至少一表面104 。該步驟可進一步包括退火處理該催化劑層1 〇8。 0992016095-0 099109016 表單編號A0101 第9頁/共27頁 201132583 [0028] 此外，若所述柔性基底102材料為一金屬片，該步驟可進 一步包括於所述金屬片之至少一表面104上預先形成一阻 隔層106後再於所述阻隔層106表面形成所述催化劑層 108。該阻隔層106可通過化學濺射、真空蒸鍍等方法形 成。該阻隔層106可防止於後續步驟五中所述金屬片與碳 源氣體發生反應，形成無定性碳，影響奈米碳管生長， 同時也防止於高溫環境下所述催化劑層1 0 8與所述柔性基 底102發生融合。該阻隔層106之材料可為矽、氮化矽、 氧化矽或金屬氧化物等。本實施例中，所述阻隔層106為 50奈米之梦層，該梦層通過磁控濺射之方法形成。 [0029] 於上述步驟二中，所述柔性基底102可通過彎曲改變自身 形狀以適應反應室120内部空間，並設置入反應室120， 優選為，通過使該柔性基底102之彎曲，使該彎曲後之柔 性基底102具有一通孔103。 [0030] 進一步地，可提供一支撐裝置130，所述已彎曲成預定形 狀之柔性基底102通過所述支撐裝置130設,置於所述反應 室120中。所述支撐裝置130包括一支撐架132，該支撐 架132之結構不限，僅需支撐且使所述柔性基底102儘量 懸空之設置於所述反應室120内即可。該支撐架132之設 置目的為使該柔性基底102設置於所述反應室120中間， 從而使該柔性基底102可被均勻加熱。 [0031] 其中，將所述柔性基底102先彎曲成一預定形狀再設置於 反應室120中之方式具體為： [0032] 首先，於一外力之作用下，將該柔性基底102從平面形狀 099109016 表單編號A0101 第10頁/共27頁 0992016095-0 201132583 結構彎曲;&-減雜。該f曲後β定雜以可容納 進所述反應室12G為准。該預定形狀<為同㈣狀、垂直 螺旋形狀 於軸向之截面具有一開口之筒形形狀、 字型形狀、或者其減則或不㈣以彡狀。優選地，該 柔性基底102f曲後形成之形狀P社面結構’即一動直 線沿著—條树平行移㈣减之#面。料曲成預定 形狀之柔性基底102具有-通孔13〇 ’該通孔從柔性基底 】〇2之一端貫穿到與其相對之另一端。The plurality of carbon nanotubes are substantially parallel to each other and grow in a direction substantially perpendicular to the smooth surface 104 of the flexible substrate 102. The substantially parallel means that most of the plurality of carbon nanotubes extend substantially in the same direction, and only a few carbon nanotubes are randomly arranged 'these carbon nanotubes do not affect most of the carbon nanotube arrays 110 The overall orientation of the rice bran tube constitutes a significant influence. The substantially vertical sun finger refers to a majority of the carbon nanotubes in the plurality of carbon nanotubes being perpendicular to the surface 104 of the inert substrate 102, and only a few of the carbon nanotubes are not completely entangled in the flexible substrate 102. And is approximately vertical, such as greater than or equal to 80 degrees and less than or equal to 1 degree. 099109016 Form No. A0101 Page / Total 27 0992016095-0 201132583 [0018] [0019] [0019]. The Heiner carbon array structure 1 further includes a catalyst layer 1〇8 disposed on at least the surface 1〇4 of the flexible substrate 102, the nanotube array 110 being formed on the catalyst layer 1〇8. The material of the catalyst layer 1〇8 may be selected from iron (Fe), the first (c〇), the recorded (Ni) or the oxide of the metal, and the catalyst layer 108 may be thermally deposited, electron beam deposited, steamed. A method such as plating or magnetron sputtering is formed on at least one surface 1〇4 of the flexible substrate 1〇2. The thickness of the catalyst layer 1 8 can be selected from the range of preferably from 1 nm to 50 nm. In this embodiment, the material of the catalyst layer 108 is iron and has a thickness of 5 nm, and the catalyst layer 1 〇 8 is disposed on one surface 1〇4 of the flexible substrate 102. In addition, if the flexible substrate 1 (32 is a metal piece, the syllabary carbon nanotube array structure 100 may further include a barrier layer disposed between the flexible substrate 1 〇 2 and the catalyst layer 108 1〇6, the material of the barrier layer 1〇6 may be cut, oxygen cut or metal oxide, etc., the barrier layer 106 has a small thickness, the thickness may be less than or equal to (10) micrometer. In the embodiment, the barrier layer The material of 106 is a layer of 5 nanometers. Since the "skin base 1G2 can be bent, the carbon nanotube array structure 100 can be a -planar structure" or can be bent into a cylindrical shape. The axial load surface has a cylindrical shape, a spiral shape, a "zi-shaped shape, or other regular or irregular shape, etc. In this embodiment, the carbon nanotube_structure has just been formed into - cylindrical shape. Since the carbon nanotube array structure 1QG has a flexible substrate (10), the carbon nanotube array structure 1 can be bent and deformed according to the needs of practical applications, thereby expanding the nanocarbon The use of the tube array structure 1〇 099109016 Form No. A01 01 Page 8 of 27 0992016095-0 201132583 [〇〇2〇] Kiss Referring to FIG. 2 and FIG. 3, the present invention provides a method for preparing the nanocarbon array structure 1 of the first embodiment described above, which comprises The following steps: [0021] Step one, providing a reaction chamber 12A and a planar flexible substrate 102 bent into a predetermined shape, the flexible substrate 2 having at least one surface 1〇4, and the flexible substrate 1〇2 Forming a catalyst layer 108 on at least one surface 1〇4; [0022] Step 2: disposing the flexible substrate 1〇2 formed with the catalyst layer 108 in the reaction chamber 120; 〇[0023] Step 3, heating station The flexible substrate 1〇2 to a predetermined waterfall degree; [0024] Step 4′, a carbon source gas is introduced into the reaction chamber 120, and at least one surface of the flexible substrate 102 is formed with a catalyst layer 1Q8. The carbon nanotube array 110. [0025] The above steps will be described in detail below. [0026] In the first step, the reaction chamber 120 may be a CVD reaction chamber 0 in the prior art. In this embodiment, the reaction Room 120 is a quartz tube furnace for CVD reaction. The chamber 120 includes an air inlet 122 and an air outlet 124 respectively disposed at two ends of the reaction chamber 120. The air inlet 122 and the air outlet 124 are located at two ends of the quartz tube furnace along the axial direction. At least one surface 104 of 102 is preferably a smooth surface. The smooth surface can be obtained by mechanical polishing or electrochemical polishing. [0027] The catalyst layer 108 can be thermally deposited, electron beam deposited, dropped or magnetron splashed. A method such as shooting is formed on at least one surface 104 of the flexible substrate 102. This step may further include annealing the catalyst layer 1 〇8. 0992016095-0 099109016 Form No. A0101 Page 9 of 27 201132583 [0028] Furthermore, if the material of the flexible substrate 102 is a metal piece, the step may further include pre-forming on at least one surface 104 of the metal piece. The catalyst layer 108 is formed on the surface of the barrier layer 106 after a barrier layer 106. The barrier layer 106 can be formed by a method such as chemical sputtering or vacuum evaporation. The barrier layer 106 prevents the metal sheet from reacting with the carbon source gas in the subsequent step 5 to form amorphous carbon, which affects the growth of the carbon nanotubes, and also prevents the catalyst layer from being in a high temperature environment. The flexible substrate 102 is fused. The material of the barrier layer 106 may be tantalum, tantalum nitride, hafnium oxide or metal oxide. In this embodiment, the barrier layer 106 is a 50 nm dream layer formed by magnetron sputtering. [0029] In the above step two, the flexible substrate 102 may be shaped to adapt to the internal space of the reaction chamber 120 by bending, and disposed in the reaction chamber 120, preferably by bending the flexible substrate 102. The rear flexible substrate 102 has a through hole 103. Further, a support device 130 may be provided, and the flexible substrate 102 that has been bent into a predetermined shape is disposed in the reaction chamber 120 by the support device 130. The supporting device 130 includes a supporting frame 132. The structure of the supporting frame 132 is not limited, and only needs to be supported and the flexible substrate 102 is suspended in the reaction chamber 120 as much as possible. The support frame 132 is disposed such that the flexible substrate 102 is disposed intermediate the reaction chamber 120 such that the flexible substrate 102 can be uniformly heated. [0031] The manner in which the flexible substrate 102 is first bent into a predetermined shape and then disposed in the reaction chamber 120 is specifically: [0032] First, the flexible substrate 102 is formed from a planar shape 099109016 under the action of an external force. No. A0101 Page 10 of 27 Page 0992016095-0 201132583 Structure bending; &- subtractive. The f-thickness β is determined to be accommodated in the reaction chamber 12G. The predetermined shape < is the same (four) shape, and the vertical spiral shape has an open cylindrical shape, a font shape, or a subtractive or not (four) shape in the axial direction. Preferably, the shape P of the flexible substrate 102f is formed in a curved shape, that is, a moving straight line is moved parallel to the strip tree (four) minus the # face. The flexible substrate 102, which is bent into a predetermined shape, has a through hole 13'' which penetrates from one end of the flexible substrate 〇2 to the other end opposite thereto.
剛請參閱圖4，當所述柔性基底102於〆外力之作用下發生 彎曲變形，且去除該外力之後，所述柔性基底102仍可保 持其彎曲之形狀時，則可首先將該彎曲後之柔性基底102 設置於所述支撐架132上，再將該設置於該支撐架132上 之柔性基底直接放置於所述反應室120中’如該柔性基底 102為被彎曲成一 “Z”型結構且去除外力之後不會恢復 成原形狀之金屬片。 [0034] 當所述柔性基底1 02於r~外力之作用下發生彎曲變形’且 去除外力之後，辦述柔性基底102又會恢復成彎曲之前之 形狀時，則所述支撐裝置130可進一步包括一固定裝置 134，於將該柔性基底1〇2設置於反應室12〇之前，採用 所述固定裝置134固定該柔性基底1〇2，從而使柔性基底 102保持彎曲後之形狀，且去除外力後該柔性基底102不 會因其固有之彈性而恢復成其彎曲前之形狀。該支撐架 132用於支撐所述固定裝置134，該固定裝置134用於固 定所述柔性基底102，該固定裝置134之形狀及設置位置 不限，可根據柔性基底102之形狀而變化，僅需使其能達 0992016095-0 099109016 表單編號A0101 第11頁/共27頁 201132583 到固定所述柔性基底102，且於步驟三加熱所述柔性基底 102時，盡可能少地阻隔熱量傳輸至所述柔性基底102即 〇 [0035] 本實施例中，所述柔性基底102被彎曲成一圓筒形形狀， 該圓筒形形狀之柔性基底102具有一通孔130，所述支撐 裝置130包括一支撐架132及設置於所述支撐架132兩端 之一固定架134。所述固定架134為兩個橫截面為圓環形 之金屬環，該彎曲成圓筒形狀之柔性基底102被固定於所 述支撐裝置130之固定架134中，即所述金屬環圍設所述 圓筒形狀之柔性基底102，使該柔性基底102固定其間。 另，該兩個固定架134相對且平行地間隔設置於所述柔性 基底102之兩端，從而使該柔性基底102之中間部分暴露 於外而不被固定架134所覆蓋。 [0036] 其次，使該彎曲後之柔性基底102設置於所述反應室120 中。優選地，使所述柔性基底102沿該反應室120之轴線 方向放置，即該柔性基底102繞該反應室120之軸線方向 彎曲，使彎曲後形成之通孔103沿該反應室120之軸線方 向放置。該設置方式可使得從進氣口 122進入反應室120 之反應氣體被柔性基底102阻擋之量最少，從而避免降低 奈米碳管之生長速度。同時，由於該柔性基底102之形狀 可被彎曲成為圓筒形狀、螺旋形形狀或其他曲面形狀， 相較於平面狀之基底，該彎曲後之柔性基底102可有效利 用該反應室120之空間，使得其可容納更大面積之柔性基 底102，從而可獲得更大面積之奈米碳管陣列110。 [0037] 此外，為使所述柔性基底102可設置於所述反應室120之 099109016 表單編號A0101 第12頁/共27頁 0992016095-0 201132583 ❹ 腔體内，該柔性基底102之厚度可依據反應室120之腔體 直徑而具體設定，具體為，若所述反應室120之腔體之直 徑為280毫米〜300毫米，且所述柔性基底102為金屬片， 則該金屬片之厚度優選小於等於1毫米，若所述柔性基底 102為石英片、矽片或陶瓷片，則所述石英片、矽片或陶 瓷片之厚度優選小於等於0. 1毫米；若所述反應室腔體之 直徑為1米，且所述柔性基底102為金屬片，則該金屬片 之厚度優選小於等於3毫米大於等於0. 1毫米，若所述柔 性基底102為石英片、矽片或陶瓷片，則所述石英片、矽 片或陶瓷片之厚度優選小於等於0. 3毫米大於等於1微米 Ο .....................................；……；；·；^·' ；0"·； V [0038] 於上述步驟三中，若所述反應室120記憶體於空氣，可進 一步包括將反應室120内之空氣排出，以防止後續步驟中 之碳源氣體與空氣發生反應，之後再加熱該筒形形狀之 柔性基底102至一預定溫度。 [0039] 〇 排出空氣之方式可包括以下三種：直接將反應室120抽真 空；向反應室120内通入保護氣體，通過該保護氣體將反 應室120内之空氣排出；另，該方式也可將反應室120抽 真空之後通入保護氣體，並使該保護氣體於該反應室120 内保持一預定之氣壓。本實施例中選擇了第三種方式。 [0040] 通入保護氣體之具體方式為：從上述進氣口 122向反應室 120内通入保護氣體，該保護氣體可選用氬氣，也可為氮 氣或其他不與後續通入之碳源氣體發生反應之氣體。該 保護氣體之輸入可使反應室120内之空氣經由該出氣口 124排出。優選地，該步驟於通入保護氣體之前先對該反 099109016 表單編號A0101 第13頁/共27頁 0992016095-0 201132583 應室120抽真空處理。於所述保護氣體之環境下，加熱該 圓筒狀之柔性基底102表面之催化劑層108至奈米碳管之 生長溫度，優選為500°C~800°C。 [0041] 於步驟四中，所述碳源氣體為乙烯、曱烷、乙烷、乙炔 或其他氣態烴類。本實施例中，該碳源氣體為乙烯。反 應時間為10分鐘〜2個小時，從而於所述柔性基底102之表 面生長獲得一奈米碳管陣列110。 [0042] 具體地，該碳源氣體和保護氣體以一預定體積比並以一 固定之流速從上述進氣口 122通入反應室120内，並同時 f 將該混合氣體以相同之流速從出氣口 124輸出反應室120 ，這樣可保持碳源氣體於反應室120内處於流動狀態-，反 應室120内參加反應之碳源氣體會得到及時之更新以使其 濃度基本維持不變，從而可得到高品質之奈米碳管陣列 110。該保護氣體與碳源氣體之體積比優選為1:〇~1:10 ，該保護氣體之流速和碳源氣體之流速依據反應室120之 腔體之具體尺寸而定。 i [0043] 於生長完奈米碳管陣列後，可將生長有奈米碳管陣列之 所述柔性基底102從所述反應室120中取出，並將該彎曲 之柔性基底102展開成平面形狀，從而獲得一平面形狀之 大面積奈米碳管陣列結構100。可見，由於該柔性基底 1 0 2於生長奈米碳管陣列11 0期間可彎曲成一預定形狀以 有效利用反應室120之空間，從而可生長出大面積之奈米 碳管陣列110，而且，當生長形成奈米碳管陣列之後，該 柔性基底102又可展開，從而改善了於曲面硬質基底上， 如螺旋形狀、“Z”字型形狀或其他規則或不規則之硬質 099109016 表單編號A0101 第14頁/共27頁 0992016095-0 201132583 [0044] ❹ [0045] 〇 生長基底上生長之奈米碳管陣列不利於實際應用之缺點 清參閱圖5 ’本發明第二實施例提供一種奈米碳管陣列結 構200 ’該奈米碳管陣列結構2〇〇包括一耐彎曲之面狀柔 性基底202 ’該柔性基底202具有至少一表面204，及至 少一奈米碳管陣列210形成於該柔性基底202之至少一表 面204 °且該奈米碳管陣列結構2〇〇可進一步包括至少一 催化劑層208和至少一阻隔層206。該奈米碳管陣列結構 200與上述第一實施例之奈米碳管陣列結構1〇〇基本相同 ’其區別於於，本實施例中之柔性基底202具有兩個表面 204 ’該兩個表面204相對設置，兩個催化劑層208分別 設置於該兩個表面204，兩個奈米碳管陣列210分別設置 於兩個催化劑層208上。 請參閱囷6，其中，第二實施例中之奈米碳管陣列結構 2〇〇之製備方法與上述第一實施例之奈米碳管陣列結構 1〇〇之製備方法基本相同，其區別於於，本實施例之步驟 一中，所提供之柔性基底202具有兩個表面2〇4，兩個催 化劑層208分別形成於所述柔性基底之兩個表面2〇4 ，當所述柔性基底202為金屬基底時，可分別於所述兩個 表面204形成兩個阻隔層2〇6，該每個阻隔層2〇6形成於 所述每個催化劑層208和每個表面204之間；於步驟二令 ，所述柔性基底202被彎油形成具有一通孔2〇3之筒形形 狀，於將該形成有催化剩層208之柔性基底2〇2設置於謗 反應室12G内之後，可進，步包括提供—加熱裝置24〇， 並將該加熱裝置240設置於該圓筒狀之柔性基底202之通 099109016 表單編號Α0101 第15頁/典27頁 〇992〇16〇95^〇 201132583 孔203内之步驟，其具體設置方式以使該整個圓筒狀之柔 性基底202均勻加熱為目的。該加熱裝置240可通過所述 圓筒狀之柔性基底2〇2之通孔203之兩端裝入該圓筒狀之 柔性基底202内。所述加熱裝置240可為電阻絲加熱管、 紅外線加熱燈管或矽钼棒加熱器等。本實施例中，所述 加熱裝置240可為一紅外線石英加熱燈管，該紅外線加熱 燈管之兩端可通過一支架250夾持並固定於圓筒狀之柔性 基底202之通孔203内。由於該反應室12〇為管式石英管 加熱爐，故本實施例中之柔性基底2〇2之兩個表面2〇4均 可被直接加熱，使該柔性基底202可快速均勻受熱，從而 使奈米碳料賴〇分卿成於所述纽基底如之兩個 表面204 〇 [0046] 本發明實關之奈$碳管_結構及⑽針法具 下優點：其-、由於所述柔性基底具有—固定之柔以 可發生彎曲’ & ’於製備奈米碳管陣列時，該、 可根據反應室之空間和自身之面積而適當二基底 形狀以有效利岐缝之錄，韻可生長^不同之 奈米碳管陣^其二、由於所述柔性基底具^面，之 柔性：故所製備之奈米碳管陣列結構可 :定之 需要被展開成—平面形狀結構或其他形狀τ、‘、、用之 管陣列結構具有較大之應用範圍。其三、所亥奈米雙 陣列直接生長於紐基底表面，以要，米後管 方法簡單。 長再轉移， [0047] 099109016 綜上所述，本發明確 出專利申請。惟，以 表單編號A0101 第16頁/共27頁 實施方 〇992〇16〇95-fl 201132583 [0048] 式，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係本發明第一實施例提供之奈米碳管陣列結構之結構 示意圖。 [0049] 圖2係本發明第一實施例之奈米碳管陣列結構之製備方法 流程圖。 〇 [0050] 圖3係本發明第一實施例之奈米碳管陣列結構之製備方法 過程示意圖。 ..... [0051] 圖4係本發明實施例製備奈米碳管陣列結構之過程中，被 彎曲成“Ζ”型形狀之柔性基底之橫截面圖。 [0052] 圖5係本發明第二實施例提供之奈米碳管陣列結構之結構 示意圖。 [0053] Ο 圖6係本發明第二實施例之奈來碳管陣列結構之製備方法 過程示意圖。 [0054] 【主要元件符號說明】 奈米碳管陣列結構：100，200 [0055] 柔性基底：102，202 [0056] 通孔：103，203 [0057] 表面：104，204 [0058] 阻隔層：106，206 099109016 表單編號Α0101 第17頁/共27頁 0992016095-0 201132583 [0059] 催化劑層：108，208 [0060] 奈米碳管陣列：110，210 [0061] 反應室：120 [0062] 進氣口 ： 122 [0063] 一 出氣口 ： 124 [0064] 支撐裝置：130 [0065] 支撐架：132 [0066] 固定裝置：134 [0067] 加熱裝置：240 [0068] 支架：250 0992016095-0 099109016 表單編號A0101 第18頁/共27頁Referring to FIG. 4, when the flexible substrate 102 is bent and deformed by the external force of the external force, and after the external force is removed, the flexible substrate 102 can still maintain its curved shape, then the bending can be first performed. The flexible substrate 102 is disposed on the support frame 132, and the flexible substrate disposed on the support frame 132 is directly placed in the reaction chamber 120 as the flexible substrate 102 is bent into a "Z" type structure and After removing the external force, it will not return to the original shape of the metal piece. [0034] When the flexible substrate 102 is subjected to bending deformation under the action of r~ external force and the external substrate is removed, and the flexible substrate 102 is restored to the shape before bending, the supporting device 130 may further include a fixing device 134 is configured to fix the flexible substrate 1〇2 by using the fixing device 134 before the flexible substrate 1〇2 is disposed in the reaction chamber 12〇, so that the flexible substrate 102 maintains the curved shape and removes the external force. The flexible substrate 102 does not return to its pre-bent shape due to its inherent elasticity. The support frame 132 is configured to support the fixing device 134. The fixing device 134 is used for fixing the flexible substrate 102. The shape and arrangement position of the fixing device 134 are not limited, and may be changed according to the shape of the flexible substrate 102. It can reach 0992016095-0 099109016 Form No. A0101 Page 11 / Total 27 Page 201132583 When the flexible substrate 102 is fixed, and the flexible substrate 102 is heated in the third step, the insulation amount is transmitted to the flexibility as little as possible. The flexible substrate 102 is bent into a cylindrical shape, the cylindrical shaped flexible substrate 102 has a through hole 130, and the supporting device 130 includes a support frame 132 and One of the fixing brackets 134 is disposed at one end of the support frame 132. The fixing frame 134 is a metal ring having a circular cross section, and the flexible substrate 102 bent into a cylindrical shape is fixed in the fixing frame 134 of the supporting device 130, that is, the metal ring enclosure The cylindrically shaped flexible substrate 102 is such that the flexible substrate 102 is secured therebetween. In addition, the two holders 134 are spaced apart from each other at opposite ends of the flexible substrate 102 such that the intermediate portion of the flexible substrate 102 is exposed to the outside without being covered by the holder 134. [0036] Next, the bent flexible substrate 102 is placed in the reaction chamber 120. Preferably, the flexible substrate 102 is placed in the axial direction of the reaction chamber 120, that is, the flexible substrate 102 is bent around the axis of the reaction chamber 120, so that the through hole 103 formed after bending is along the axis of the reaction chamber 120. Place in the direction. This arrangement allows the amount of reactant gas entering the reaction chamber 120 from the inlet 122 to be blocked by the flexible substrate 102 to a minimum, thereby avoiding a reduction in the growth rate of the carbon nanotubes. Meanwhile, since the shape of the flexible substrate 102 can be bent into a cylindrical shape, a spiral shape or other curved shape, the curved flexible substrate 102 can effectively utilize the space of the reaction chamber 120 compared to the planar substrate. It allows it to accommodate a larger area of flexible substrate 102 so that a larger area of carbon nanotube array 110 can be obtained. [0037] In addition, in order to enable the flexible substrate 102 to be disposed in the reaction chamber 120, 099109016, Form No. A0101, Page 12 / Total 27, 0992016095-0 201132583, the thickness of the flexible substrate 102 can be determined according to the reaction. The cavity diameter of the chamber 120 is specifically set. Specifically, if the diameter of the cavity of the reaction chamber 120 is 280 mm to 300 mm, and the flexible substrate 102 is a metal piece, the thickness of the metal piece is preferably less than or equal to 1毫米; if the flexible substrate 102 is a quartz plate, a slab or a ceramic plate, the thickness of the quartz plate, the slab or the ceramic plate is preferably less than or equal to 0.1 mm; if the diameter of the reaction chamber cavity is 1毫米。 If the flexible substrate 102 is a metal piece, the thickness of the metal piece is preferably less than or equal to 3 mm or more than 0.1 mm, if the flexible substrate 102 is a quartz piece, a cymbal piece or a ceramic piece, The thickness of the quartz piece, the cymbal piece or the ceramic piece is preferably less than or equal to 0.3 mm or more and 1 micron Ο ............................ .........;......;;;;··· ;0"·; V [0038] In the above step three, if the opposite Memory 120 to the air chamber may further include an air discharge within the reaction chamber 120, in order to prevent the carbon source gas and air occurs subsequent step of the reaction and then heating the flexible substrate 102 of the cylindrical shape to a predetermined temperature. [0039] The manner of exhausting air may include the following three types: directly evacuating the reaction chamber 120; introducing a shielding gas into the reaction chamber 120, and discharging the air in the reaction chamber 120 through the shielding gas; After the reaction chamber 120 is evacuated, a shielding gas is introduced, and the shielding gas is maintained at a predetermined gas pressure in the reaction chamber 120. The third mode is selected in this embodiment. [0040] The specific manner of introducing the shielding gas is: introducing a shielding gas into the reaction chamber 120 from the air inlet 122, and the shielding gas may be argon gas, nitrogen gas or other carbon source that is not connected to the subsequent gas. The gas in which the gas reacts. The input of the shielding gas allows the air in the reaction chamber 120 to be discharged through the air outlet 124. Preferably, the step is to vacuum the chamber 120 before the protection gas is introduced to the counter 099109016, form number A0101, page 13 of 27, and 0992016095-0 201132583. The growth temperature of the catalyst layer 108 to the carbon nanotubes on the surface of the cylindrical flexible substrate 102 is heated in an atmosphere of the shielding gas, preferably 500 ° C to 800 ° C. [0041] In the fourth step, the carbon source gas is ethylene, decane, ethane, acetylene or other gaseous hydrocarbons. In this embodiment, the carbon source gas is ethylene. The reaction time is from 10 minutes to 2 hours to obtain a carbon nanotube array 110 on the surface of the flexible substrate 102. [0042] Specifically, the carbon source gas and the shielding gas are introduced into the reaction chamber 120 from the inlet port 122 at a predetermined volume ratio and at a fixed flow rate, and at the same time, the mixed gas is discharged at the same flow rate. The gas port 124 outputs the reaction chamber 120, so that the carbon source gas can be kept in the flow state in the reaction chamber 120. The carbon source gas participating in the reaction in the reaction chamber 120 is updated in time to maintain the concentration substantially unchanged, thereby obtaining High quality carbon nanotube array 110. The volume ratio of the shielding gas to the carbon source gas is preferably 1: 〇~1:10, and the flow rate of the shielding gas and the flow rate of the carbon source gas depend on the specific size of the cavity of the reaction chamber 120. [0043] After the carbon nanotube array is grown, the flexible substrate 102 on which the carbon nanotube array is grown can be taken out from the reaction chamber 120, and the curved flexible substrate 102 can be expanded into a planar shape. Thereby, a large-area carbon nanotube array structure 100 of a planar shape is obtained. It can be seen that since the flexible substrate 102 can be bent into a predetermined shape during the growth of the carbon nanotube array 11 0 to effectively utilize the space of the reaction chamber 120, a large-area carbon nanotube array 110 can be grown, and After growing to form the carbon nanotube array, the flexible substrate 102 can be expanded again, thereby improving on a curved hard substrate, such as a spiral shape, a "Z" shape or other regular or irregular hard 099109016 Form No. A0101 No. 14 Page / Total 27 pages 0992016095-0 201132583 [0044] [0045] The carbon nanotube array grown on the growth substrate is disadvantageous for practical application. Referring to FIG. 5, a second embodiment of the present invention provides a carbon nanotube. Array structure 200' The carbon nanotube array structure 2 includes a curved, flexible planar substrate 202. The flexible substrate 202 has at least one surface 204, and at least one carbon nanotube array 210 is formed on the flexible substrate 202. At least one surface 204° and the carbon nanotube array structure 2 〇〇 may further include at least one catalyst layer 208 and at least one barrier layer 206. The carbon nanotube array structure 200 is substantially identical to the carbon nanotube array structure 1 of the first embodiment described above, which is different from the flexible substrate 202 of the present embodiment having two surfaces 204' 204 is oppositely disposed, two catalyst layers 208 are respectively disposed on the two surfaces 204, and two carbon nanotube arrays 210 are respectively disposed on the two catalyst layers 208. Please refer to FIG. 6 , wherein the preparation method of the carbon nanotube array structure 2 in the second embodiment is substantially the same as the preparation method of the carbon nanotube array structure 1 in the first embodiment, which is different from In the first step of the embodiment, the flexible substrate 202 is provided with two surfaces 2〇4, and two catalyst layers 208 are respectively formed on the two surfaces 2〇4 of the flexible substrate, when the flexible substrate 202 is In the case of a metal substrate, two barrier layers 2〇6 may be formed on the two surfaces 204, respectively, and each barrier layer 2〇6 is formed between each of the catalyst layers 208 and each surface 204; Secondly, the flexible substrate 202 is formed into a cylindrical shape having a through hole 2〇3 by bending oil, and after the flexible substrate 2〇2 formed with the catalytic remaining layer 208 is disposed in the crucible reaction chamber 12G, it can be advanced. The step includes providing a heating device 24, and placing the heating device 240 on the cylindrical flexible substrate 202. 099109016 Form No. Α0101 Page 15 / Code 27 〇992〇16〇95^〇201132583 Hole 203 Step, which is specifically set up to make the whole circle Like the flexible substrate 202 for the purpose of uniform heating. The heating device 240 is inserted into the cylindrical flexible substrate 202 through both ends of the through hole 203 of the cylindrical flexible substrate 2〇2. The heating device 240 may be a resistance wire heating tube, an infrared heating tube or a bismuth molybdenum rod heater or the like. In this embodiment, the heating device 240 can be an infrared quartz heating lamp tube. Both ends of the infrared heating lamp tube can be clamped and fixed in the through hole 203 of the cylindrical flexible substrate 202 through a bracket 250. Since the reaction chamber 12 is a tubular quartz tube heating furnace, both surfaces 2〇4 of the flexible substrate 2〇2 in the embodiment can be directly heated, so that the flexible substrate 202 can be heated uniformly and uniformly, thereby The nano carbon material is formed on the surface of the new substrate such as the two surfaces 204 〇 [0046] The present invention is a solid carbon nanotube _ structure and (10) needle method has the following advantages: - due to the flexibility The substrate has a fixed softness to bend [&', when preparing the carbon nanotube array, the shape of the reaction chamber can be appropriately determined according to the space of the reaction chamber and the area of the reaction chamber, and the rhyme can be effectively recorded. Growth of different carbon nanotube arrays. Second, because the flexible substrate has a flexible surface: the prepared carbon nanotube array structure can be: it needs to be expanded into a planar shape structure or other shape τ The ',, and tube array structure used has a large application range. Thirdly, the double array of Heinami directly grows on the surface of the New substrate, so that the method of the rice back tube is simple. Long re-transfer, [0047] 099109016 In summary, the present invention identifies a patent application. However, the form number A0101 can be used 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 view showing the structure of a carbon nanotube array structure according to a first embodiment of the present invention. 2 is a flow chart showing a method of preparing a carbon nanotube array structure according to a first embodiment of the present invention. 3 is a schematic view showing a process for preparing a carbon nanotube array structure according to a first embodiment of the present invention. [0051] Figure 4 is a cross-sectional view of a flexible substrate bent into a "Ζ" shape during the preparation of a carbon nanotube array structure in accordance with an embodiment of the present invention. 5 is a schematic view showing the structure of a carbon nanotube array structure according to a second embodiment of the present invention. [0053] FIG. 6 is a schematic view showing a process for preparing a carbon nanotube array structure according to a second embodiment of the present invention. [Main Element Symbol Description] Carbon nanotube array structure: 100,200 [0055] Flexible substrate: 102, 202 [0056] Through hole: 103, 203 [0057] Surface: 104, 204 [0058] Barrier layer :106,206 099109016 Form No. 1010101 Page 17 of 27 0992016095-0 201132583 [0059] Catalyst layer: 108, 208 [0060] Carbon nanotube array: 110, 210 [0061] Reaction chamber: 120 [0062] Air inlet: 122 [0063] One air outlet: 124 [0064] Supporting device: 130 [0065] Support frame: 132 [0066] Fixing device: 134 [0067] Heating device: 240 [0068] Bracket: 250 0992016095-0 099109016 Form No. A0101 Page 18 of 27