201043568 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種奈米碳管結構之製備方法，尤其涉及— 種奈米碳管膜之製備方法。 [先前技術] [0002] 奈米碳管（Carbon Nanotube，CNT)係一種新型碳材料 ，曰本研究人員Iijima於1991年首次於實驗室製備獲得 (請參見，Helical Microtubules of Graphitic201043568 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a method for preparing a carbon nanotube structure, and more particularly to a method for preparing a carbon nanotube film. [Prior Art] [0002] Carbon Nanotube (CNT) is a new type of carbon material, which was first prepared by the researcher Iijima in the laboratory in 1991 (see, Helical Microtubules of Graphitic).
Carbon’ Nature， Vol. 354， P56-58 (1991))。奈 米碳管之特殊結構決定了其特殊之拄質，知高抗張強度 與高熱穩定性。根據奈米碳管螺旋方式之不同，奈米礙 管呈現出金屬性或半導體性等。由於奈米碳管具有良好 之力學、電學、熱學等性質以及理想之一維結構，其在 材料科學、化學、物理學等交叉學科領域已展現出廣闊 之應用前景，尤其係場發射平板顯示，電子器件，原子 力顯微鏡（Atomic Force Microscopf AFM)針尖，熱 感測器’光學感測器，過濾器等方面。 [0003] 雖然奈米碳管性能優異，具有廣泛之應用，然，一般情 況下製備得到之奈米碳管在宏觀上為顆粒狀或粉末狀， 不利於奈米碳管之宏觀應用。因此製備各種宏觀之奈米 碳管結構，尤其係製備具有宏觀性質之奈米碳管媒成為 人們關注之熱點。 [0004] 先前之製備奈米碳管膜之方法包括直接生長法、噴塗法 或朗缪爾布洛節塔（Langmuir Blodgett, LB)法。其 中，直接生長法通過控制反應條件，如以硫磺作為添加 098118658 表單編號A0101 第4頁/共28頁 0982031622-0 201043568 〇 劑或設置多層催化劑等，藉由化學氣減積法直 付到奈米碳管膜；其—般包括以下步驟：提供—生長基 底；在該生長基底沈積一催化綱；提供—反應爐= 將該沈積有催化觸之生長基底置於所述反應爐内；通 入碳源氣，並加熱以生長奈米碳管膜。嘴塗法一般藉由 將奈米碳管粉末形成水性紐並Μ於-基材表面，經 乾燥後形成奈米碳管膜結構。LB法-般藉由將_奈米碳 管溶液混入另-具有不同密度之溶液（如有機溶劑）中 ’利用分子自組裝運動，奈米碳管浮出溶液表面形成奈 米碳管膜。 [0005] 然而，上述藉由直接生長法或喷塗法獲得之奈米碳管膜 中，奈米碳管往往容易聚集成團，導致奈米碳管膜厚度 不均。上述藉由LB法製備得到之奈米碳管膜結構一般為 均勻網狀結構，奈米碳管分散均勻，不團聚。惟，奈米 碳管在膜中仍然為無序排列，不利於充分發揮奈米碳管 之性能，如：導電性與導熱性，其應用仍蠢受到限制。 〇 [0006] 為解決上述問題，Baughman Ray Η.等人於2005年11 月9日申請的’ 2007年2月8日公開的，公開號為w〇 2007/01 5710 A2,標題為 “THE FABRICATION AND APPLICATION OF NANOFIBER RIBBONS AND SHEETS AND TWISTED AND NONTWISTED NANOFIBER YARNS*1 之PCT國際專利申請中揭示了 一種奈米纖維膜之製備方法 。該奈米纖維膜之製備方法包括以下步驟：提供一奈米 纖維陣列，該奈米纖維陣列中之奈米纖維基本平行排列 ;從上述奈米纖維陣列中拉伸上述奈米纖維，得到一奈 098118658 表單編號A0101 第5頁/共28頁 0982031622-0 201043568 米纖維膜。其中，所述奈米纖維陣列為近似圓柱形之奈 米纖維陣列。 [0007] 從所述奈米纖維陣列中拉膜時，該奈米纖維膜之起始寬 度與被拉伸處之奈米纖維之寬度一致。然，被拉伸處之 奈米纖維之寬度不可避免的會受到圓柱形奈米纖維陣列 之影響，從而造成該奈米纖維膜之寬度不會一致，其形 狀不規則，不利於工業化應用。 【發明内容】 [0008] 有鑒於此，確有必要提供一種寬度基本相同，形狀基本 規則，有利於工業化應用之奈米碳管膜之製備方法。 [0009] 一種奈米碳管膜之製備方法，其包括以下步驟：提供一 基底，該基底具有一表面；於所述基底之表面形成一具 有兩個相互平行之邊的催化劑層；將形成有所述催化劑 層之基底於高溫空氣中退火；將退火後之基底置於反應 爐中，於保護氣體環境下加熱到 [0010] 700°C至1 000°C，然後通入碳源氣反應一段時間，生長得 到一奈米碳管陣列，該奈米碳管陣列有兩個基本平行之 側面，該兩個側面與所述催化劑層之兩個相互平行之邊 對應；以及從所述奈米碳管陣列中沿與所述兩個侧面平 行之方向拉取奈米碳管，獲得一奈米碳管膜。 [0011] 與先前技術相比較，所述奈米碳管膜製備方法藉由奈米 碳管陣列有兩個相互平行之側面，沿平行於該侧面之方 向拉膜，即可得到具有相同寬度且形狀規則之奈米碳管 膜，有利於工業化應用。 098118658 表單編號A0101 第6頁/共28頁 0982031622-0 201043568 [0012] [0013] Ο [0014]Ο [0015] 【實施方式】 下面將結合附圖及具體實施例，對本發明提供之奈米碳 音膜之製備方法作進一步之詳細說明。 凊參閱圖1，本發明第一實施例提供一種奈米碳管膜之製 備方法，該奈米碳管膜之製備方法主要包括以下步驟： (al)提供一基底，該基底具有一表面；（a2)於所述 基底之表面形成一具有兩個相互平行之邊的催化劑層； (a3)將形成有所述催化劑層之基底於高溫空氣中退火 ，（a4)將退火後之基底置於反應爐中，於保護氣體環 境下加熱到70(TC至l〇〇〇°c，然後通入碳源氣反應一段時 間’生長得到^奈米碳管陣列，該奈米碳管陣列有兩個 基本平行之侧面’該兩個側面與所述催化劑層之兩個相 互平行之邊對應；（a5)從所述奈米碳管陣列中沿與所 述兩個側面平行之方向拉取奈米碳管，獲得一奈米碳管 膜。 請參閱圖2至圖4,於步驟（ai)中，提供一基底12，該 基底12具有一表面122。該基底12為平整之圓形基底，其 材料為玻璃、石英、矽或氧化鋁。本實施例採用4英寸之 平整光滑之矽基底。 於步驟（a2)中，於所述基底12之表面122形成一具有兩 個相互平行之邊的催化劑層14，形成該催化劑層14之方 法包括基底處理法或催化劑層處理法。所述基底處理法 包括：對所述基底12之表面122進行處理，在該基底12之 表面122形成一獨立的具有兩個相互平行邊的生長表面； 在該基底12之生長表面形成催化劑層14。所述催化劑層 098118658 表單編號A0101 第7頁/共28頁 0982031622-0 201043568 處理法包括模板法、光刻法等。所述模板法包括以下步 驟：提供一掩模板，該掩模板包括一遮蔽部分及由該遮 蔽部分限定之鏤空部分，該鏤空部分具有兩個相互平行 之邊，藉由所述掩模板在所述基底12之表面122形成—催 化劑層14，使該催化劑層14具有兩個相互平行之邊。所 述光刻法包括以下步驟：於所述基底12之表面122形成一 催化劑層14 ;對該催化劑層14進行光刻處理，使該催化 劑層14具有兩個相互平行之邊。其中，所述催化劑層i 4 由兩個相互平行之邊及連接該兩個邊之邊限定。 [00161 本實施例採用模板法於所遂基底12之表面12 2形成—具有 兩個相互平行之邊的催化劑層14。具艏地，所述模板法 包括以下步驟：首先’提供一掩模板2〇，該掩模板2〇包 括一遮蔽部分22及由該遮蔽部分22限定之鏤空部分24。 其中’所述掩模板20之材料不限，只要其在後續過程中 不會發生變形即可。所述垮模板20之材料優選為金屬材 ... .. 料。所述掩模板2〇之鐘空珠分24具貪兩锢相互平行之邊 . . ..丨.. 。本實施例中’所述掩模板20之材料為鐵。所述掩模板 20之鏤空部分24之形狀為長方形。 [0017] 可以理解’所述掩模板20之鏤空部分24之形狀不限於上 述實施例，其還可以為其他具有兩個相互平行之邊的形 狀，如“U”型或其他形狀。 [0018] 其次’將該掩模板20與所述基底12間隔設置，使該掩模 板20之鏤空部分24之正投影完全落在所述基底12上。其 中，所述掩模板20與所述基底12之間之間隔大於0. 1毫米 ，且小於等於100毫米。優選地，該掩模板20與所述基底 098118658 表單編號 A0101 第 8 頁/共 28 頁 0982031622-0 201043568 12之間之間隔大於〇· 1毫来，且小於等於丨〇毫米。本實施 例中’所述掩模板20與所述基底12之間之間隔為2毫米。 [0019] 然後，藉由所述掩模板20之鏤空部分24於所述基底12形 成一催化劑層14，該催化劑層14具有兩個相互平行之邊 。其中’所述催化劑層14之形狀與所述掩模板20之鏤空 部分之形狀對應。所述催化劑層14之厚度為2奈米至9奈 米’該催化劑層14之材料為鐵（Fe)、鈷（Co)、鎳（ Ni)等金屬或其任意组合之合金。所述催化劑層η之形 成方法包括蒸鍍法、熱沈積法、電子束沈積法或濺射法 。本實施例中’所述催化劑層14之厚度為3奈米至6奈米 ’該催化劑層14之材料為鐵。所述催化劑層η之形成方 法為蒸鍍法。本實施例中，由於所述掩模板2〇之鏤空部 分24之形狀為長方形，所以形成於基底12之催化劑層14 也為長方形。 [0020] 最後’去除掩模板2 [0021] 於步驟（a3)中，將杉成有所述催化劑層14之基底12於 高溫空氣中退火約30分鐘至90分鐘，使該催化劑層14氧 化成粒fe分佈較為集中之奈米級催化劑顆粒層。 [0022] 於步驟（a4)中，將退火後之基底12置於反應爐中，於 保護氣體環境下加熱到7〇(pCi1〇〇(rc，然後通入碳源氣 反應一段時間’得到一奈米碳管陣列1〇。由於該奈米碳 管陣列10於平行於基底12之表面122之平面内具有至少兩 相對平行之邊與所述催化劑層14之相互平行之邊對應， 且該奈米破管陣列10具有一定高度，所以該奈米碳管陣 098118658 表單編號A0101 第9頁/共28頁 0982031622-0 201043568 列10有兩個基本平行之側面2與側面4，該側面2、側面4 與所述催化劑層14之兩個相互平行之邊對應。其中，所 述保護氣體為氦氣、氖氣、氬氣或氪氣等惰性氣體。所 述碳源氣為乙炔、乙烯或甲烷等碳氫化合物。本實施例 中，所述保護氣體為氬氣；所述碳源氣為乙炔；所述通 入碳源氣體之進行反應之時間為5分鐘至30分鐘；所述奈 米碳管陣列之高度為200微米至400微米。 [0023] 所述奈米碳管陣列1 0由多個奈米碳管組成，該多個奈米 碳管為單壁奈米碳管、雙壁奈米碳管及多壁奈米碳管中 之一種或多種。本實施例中，該多個奈米碳管為多壁奈 米碳管，且該多個奈米碳管基本上相互平行且垂直於所 述基底12，即該奈米碳管陣列10為超順排之多壁奈米碳 管陣列。 [0024] 本實施例中，由於催化劑層14之形狀為長方形，所以， 所述奈米碳管陣列10包括分別相對設置且基本平行之側 面2與側面4、側面6與侧面8。藉由控制所述生長條件， 該奈米碳管陣列10中基本不含有雜質，如無定型碳或殘 留之催化劑金屬顆粒等。 [0025] 於步驟（a5)中，首先，提供一拉伸工具26，將該拉伸 工具26與所述奈米碳管陣列10中奈米碳管相接觸並形成 一接觸面，優選地，該接觸面與該奈米碳管陣列10相互 平行之兩個侧面2、侧面4垂直且接觸。其中，所述拉伸 工具26之長度大於等於所述奈米碳管陣列10之相互平行 之侧面2、側面4之間之垂直距離。本實施例中，所述拉 伸工具26為一膠帶，該膠帶與所述奈米碳管陣列10之接 098118658 表單編號A0101 第10頁/共28頁 0982031622-0 201043568 [0026] Ο ❹ [0027] [0028] 098118658 觸處之多個奈米碳管相黏結形成—接觸面，且該膠帶之 長度略大於該奈米碳管陣列10之相互平行之側面2與側面 4之間之垂直距離。 其次，沿基本上與所述奈米碳管陣列1〇之兩個相互平行 之側面平仃’且與所述基底12成預定角度之方向拉伸該 奈米碳營陣列10，與所述拉伸工具26黏結之多個奈米碳 管在拉力作用下沿拉伸方向逐漸脫離基底12，同時，由 於凡德瓦爾力作用，該選定之多個奈米碳管分別與其他 不米碳g首尾相連地連續地被拉出。由於所述奈米碳管 陣列10之相互平行之兩個側面2、側面4之間的距離基本 上係相同的’從而形成—連續的、具有相同寬度且形狀 規則之V,碳管膜28。同時.，該㈣碳㈣28還具有良 好之連續性及均勻性。其中，該奈米碳管膜28中奈米碳 管之^方向基本平行於該奈米碳管膜之拉伸方向。所 述預疋角度之範圍為大於〇。，且小於等於3〇。，優選為大 於0 ’且小於等於5。。 所述奈米碳管膜28之長度不限，可根據實際需求制得。 ^米碳㈣㈣輪㈣婦陣心之形 =。本實施例中’所述拉伸工具26沿與該奈米碳管 車列10之側面2、側面4平扞 。 仃之方向，且與所述基底12成5 °拉伸該黏結處之多個奈米碳管。 第二實施例提供〜種奈米碳管臈之製備方法，該 =法主要包括以下步輝：（b"提供一基底，該基 表面；⑽，所述基底之表面形成一具有兩 表單編號^之邊的第催7層；⑻）將形成有所述催化 嚴/共28頁 0982031622-0 201043568 劑層之基底於高溫空氣中退火；（b4)將退火後之基底 置於反應爐中’於保護氣體環境下加熱到700°c至100(TC ，然後通入碳源氣反應一段時間，生長得到一奈米碳管 陣列’該奈米碳管陣列有兩個基本平行之側面，該兩個 侧面與所述催化劑層之兩個相互平行之邊對應；（b5) 從所述奈米碳管陣列中沿與所述兩個側面平行之方向拉 取奈米碳管，獲得一奈米碳管膜。該製備方法與第一實 施例提供之奈米碳管膜之方法基本相同，不同之處在於 .本實施例中之步驟（b2)之具體步驟與第一實施例中 . ...... . . 之步驟（a2)之具體步驟不同。 [0029] [0030] [0031] 098118658 凊一併參閱圖5和圖8，於步驟（bl )中，提供一基底32 ，忒基底32具有一表面322 »該基底32之材料及形狀與第 一實施例中之基底12之材料及形狀相同。 於步驟（b2)中，於所述基底32之表面322形成一具有兩 3 4，形成該催化劑層3 4之方 法為基底處理法。該基底處理法包括以下步驟：對所述 基底32之表面322進行處理，於該辱底32之表面322形成 獨立之具有兩個相互平行邊之生長表面320 ;於該基底 32之生長表面320形成催化劑層34。 其中’於所述基底32之表面322形成獨立之具有兩個相互 平行邊之生長表面320之方法具體包括：採用光刻法或雷 射法於所述基底表面322形成至少兩個相互平行之凹押 324 ’位於兩平行凹槽324之間之基底表面322為生長表 面320 ’該生長表面320與該基底表面322之剩餘表面326 藉由凹槽324分離。圖6所示之基底32之形狀係藉由上述 表單編號A0101 第12頁/共28頁 0982031622-0 201043568 方法形成的。_6中之基底32之形狀為：所述基底表面 322形成兩對相互平行之凹槽324，生長表面320通過該 兩對相互平行之凹槽324與剩餘表面326分離，且該生長 表面320之形狀為長方形。 剛此外，也可簡由光刻法或雷射法去除部分上述基底表 面322之剩餘表面326，使該剩餘表面326之厚度減薄， 於所述基底32之表面322形成獨立之具有兩個相互平行邊 之生長表面320。圖7所示之基底32之形狀就係藉由該方 〇 法形成的圖7中之基底32之形狀為：所述剩餘表面326 之厚度減薄，使得長方形之生長表面32〇突出該剩餘表面 326。 ' 剛料藉由細料雷射衫全擔上述基底表 面322之嶋表面㈣，於所述基底32之表面奶形成獨 立之具有兩個相互平行邊之生長表面3膊。圖8所示之基 底32之形狀就係藉由該方法形成的。圖8中的生長表面 320為長方形，基底32為長方體形。 〇 剛本實施例中，採用雷射法在基底32之表面322上形成一獨 立之生長表面320。具體地，首先，提供一雷射器，該雷 射器之雷射光束之照射路徑可藉由電腦程式控制。其次 將基底32之开>狀輸入電腦程式中，以便控制雷射器中 之雷射光束之照射路徑，於所述基底32之表面322形成生 長表面320。然後，開啟雷射器，採用雷射光束照射所述 基底32之表面322，且使雷射光束沿圖5中之虛線照射該 基底32之表面322，切除所述基底32之剩餘表面326對應 之部分，得到生長表面320，使得該基底32之形狀變為長 0982031622-0 098118658 表單編號A0101 第13頁/共28頁 201043568 方體形，如圖8所示之形狀。可以理解，還可以藉由固定 雷射光束，移動基底32使雷射光束照射該基底32之表面 322，控制該基底32之運動路徑，將該基底32燒蝕成長方 體。 [0035] 可以理解，所述生長表面320之形狀不限於第二實施例， 其還可以為其他有兩個相互平行之邊的形狀，如，“U” 型或其他形狀。 [0036] 於步驟（b3)中，將形成有催化劑層34之基底32於高溫 空氣中退火約30分鐘至90分鐘，使該催化劑層34氧化成 粒徑分佈較為集中之奈米級催化劑顆粒層。 [0037] 於步驟（b4)中，將退火後之基底32置於反應爐中，於 保護氣體環境下加熱到700至1 000°C，然後通入碳源氣反 應一段時間，得到一奈米碳管陣列30。本實施例中之保 護氣體、碳源氣、該碳源氣反應時間、奈米碳管陣列30 之高度及形狀分別與第一實施例中之保護氣體、碳源氣 、該碳源氣反應時間、奈米碳管陣列1 0之高度及形狀相 同。 [0038] 於步驟（b5)中，從所述奈米碳管陣列30中沿與所述兩 個相互平行之侧面平行之方向拉取一奈米碳管膜3 8。該 步驟（b5)之具體方法與第一實施例步驟（a5)之具體 方法相同。 [0039] 本發明實施例提供之奈米碳管膜之製備方法，具有以下 優點：藉由處理催化劑層或基底使得該製備方法中之奈 米碳管陣列有兩個相互平行之側面，所以沿平行於該側 098118658 表單編號A0101 第14頁/共28頁 0982031622-0 201043568 面之方向拉取多個奈米裙故 &，即可得到具有良好之均勻 、相同之寬度且形狀規則 』之不水妷管膜。該方法簡單 易仃，而且成本低，且讀秦 木妷管膜無需後續處理，可 以於工業上直接應用，有 呀利於在工業上大規模生產。 [0040] 综上所述，本發明確已将 〇發明專利之要件，遂依法提 出專利申請。惟’以上所奸、i 丨处者僅為本發明之較佳實施例 ’自不能以此限制本案之由μ 晴專利範圍。舉凡熟悉本案 技藝之人士援依本發明之杜& ^積砷所作之等效修飾或變化， Ο 皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 _] 11係本發明第—實施例提供之奈米碳管膜之製備方法流 程圖。 [0042] 圖2係本發明第一實施例提供之用於製備奈米碳管膜之生 長有奈米碳管陣列之基底之側視圖。 Ο [0043] 圖3係本發明第一實施例提供之用於製備奈米碳管膜之生 長有奈米碳管陣列之基底之俯視圖。 [0044] 圖4係本發明第一實施例提供之奈米碳管膜之製備工藝流 程圖。 [0045] 圖5係本發明第二實施例提供之奈米碳管膜之製備工藝流 程圖。 [0046] 圖6、圖7與圖8係本發明實施例提供之具有生長表面之基 底之形狀示意圖。 【主要元件符號說明】 098118658 表單編號A0101 第15頁/共28頁 0982031622-0 201043568 側面 2 ； 4 ； 6 ； 8 奈米碳管陣列 10 ； 30 基底 12 ； 32 基底之表面 122 ； 322 催化劑層 14 ； 34 掩模板 20 掩模板之遮蔽部分 22 掩模板之鏤空部分 24 拉伸工具 26 奈米碳管膜 28 ； 38 生長表面 320 凹槽 324 剩餘表面 32 6 ' 098118658 表單編號A0101 第16頁/共28頁 0982031622-0Carbon’ Nature, Vol. 354, P56-58 (1991)). The special structure of the carbon nanotubes determines its special enamel, high tensile strength and high thermal stability. Depending on the way in which the carbon nanotubes are spiraled, the nanotubes are metallic or semiconducting. Because the carbon nanotubes have good mechanical, electrical, thermal and other properties and ideal one-dimensional structure, they have shown broad application prospects in the fields of materials science, chemistry, physics and other interdisciplinary fields, especially the field emission flat panel display. Electronic devices, Atomic Force Microscopf AFM tip, thermal sensor 'optical sensor, filter, etc. [0003] Although the performance of the carbon nanotubes is excellent and has a wide range of applications, the carbon nanotubes prepared in the general case are macroscopically granular or powdery, which is disadvantageous for the macroscopic application of the carbon nanotubes. Therefore, the preparation of various macroscopic carbon nanotube structures, especially the preparation of nanocarbon tubes having macroscopic properties, has become a hot spot of concern. [0004] Previous methods for preparing carbon nanotube membranes include direct growth, spray coating or Langmuir Blodgett (LB). Among them, the direct growth method is controlled by the reaction conditions, such as sulfur as an additive 098118658 Form No. A0101 Page 4 / 28 pages 0982031622-0 201043568 Tanning agent or multi-layer catalyst, etc., by chemical gas deduction method directly paid to the nanometer a carbon tube film; generally comprising the steps of: providing a growth substrate; depositing a catalytic element on the growth substrate; providing a reaction furnace = placing the deposition substrate having the catalytic contact in the reaction furnace; and introducing carbon into the reaction furnace; The source gas is heated and grown to grow a carbon nanotube film. The mouth coating method generally forms a carbon nanotube film structure by drying the carbon nanotube powder into an aqueous layer and rubbing it on the surface of the substrate. The LB method generally uses a molecular self-assembly motion by mixing a solution of the carbon nanotubes into another solution having a different density (e.g., an organic solvent), and the carbon nanotubes float out of the surface of the solution to form a carbon nanotube film. [0005] However, in the above-described carbon nanotube film obtained by the direct growth method or the spray coating method, the carbon nanotubes tend to aggregate easily, resulting in uneven thickness of the carbon nanotube film. The structure of the carbon nanotube film prepared by the LB method is generally a uniform network structure, and the carbon nanotubes are uniformly dispersed and do not agglomerate. However, the carbon nanotubes are still disorderly arranged in the film, which is not conducive to the full play of the performance of the carbon nanotubes, such as conductivity and thermal conductivity, and its application is still stupid. 〇[0006] In order to solve the above problem, Baughman Ray Η. et al., published on November 9, 2005, published on February 8, 2007, published under the number w〇2007/01 5710 A2, entitled "THE FABRICATION A method for preparing a nanofiber membrane is disclosed in the PCT International Patent Application No. RIBBONS AND SHEETS AND TWISTED AND NONTWISTED NANOFIBER YARNS*1. The method for preparing the nanofiber membrane comprises the steps of: providing a nanofiber array The nanofibers in the nanofiber array are arranged substantially in parallel; the nanofibers are stretched from the nanofiber array to obtain a 奈 098118658 Form No. A0101 Page 5 / 28 pages 0982031622-0 201043568 Wherein the nanofiber array is an approximately cylindrical nanofiber array. [0007] When the film is pulled from the nanofiber array, the initial width of the nanofiber film and the stretched portion of the nanofiber film The width of the rice fibers is the same. However, the width of the nanofibers to be stretched is inevitably affected by the array of cylindrical nanofibers, resulting in the width of the nanofiber membrane. It is not consistent, and its shape is irregular, which is not conducive to industrial application. [Invention] [0008] In view of this, it is indeed necessary to provide a carbon nanotube film having substantially the same width and basic shape and favorable for industrial application. [0009] A method for preparing a carbon nanotube film, comprising the steps of: providing a substrate having a surface; forming a catalyst layer having two parallel sides on the surface of the substrate; The substrate on which the catalyst layer is formed is annealed in high temperature air; the annealed substrate is placed in a reaction furnace, heated to [0010] 700 ° C to 1 000 ° C under a protective gas atmosphere, and then passed through a carbon source gas. Reacting for a period of time, growing to obtain an array of carbon nanotubes having two substantially parallel sides, the two sides corresponding to two mutually parallel sides of the catalyst layer; The carbon nanotube film is drawn in a direction parallel to the two sides in the carbon nanotube array to obtain a carbon nanotube film. [0011] Compared with the prior art, the carbon nanotube film preparation method By having two mutually parallel sides of the carbon nanotube array and pulling the film in a direction parallel to the side, a carbon nanotube film having the same width and regular shape can be obtained, which is advantageous for industrial applications. 098118658 Form No. A0101 6 pages / 28 pages 0982031622-0 201043568 [0013] [0014] [Embodiment] Hereinafter, a method for preparing a nano carbon sound film provided by the present invention will be described with reference to the accompanying drawings and specific embodiments. For further details. Referring to FIG. 1, a first embodiment of the present invention provides a method for preparing a carbon nanotube film. The method for preparing the carbon nanotube film mainly comprises the following steps: (a) providing a substrate having a surface; A2) forming a catalyst layer having two mutually parallel sides on the surface of the substrate; (a3) annealing the substrate on which the catalyst layer is formed in high temperature air, and (a4) placing the annealed substrate in the reaction In the furnace, heated to 70 (TC to l〇〇〇 °c in a protective gas atmosphere, and then passed into the carbon source gas for a period of time to grow to obtain a carbon nanotube array, the carbon nanotube array has two basic Parallel sides 'the two sides correspond to two mutually parallel sides of the catalyst layer; (a5) pulling the carbon nanotubes from the array of carbon nanotubes in a direction parallel to the two sides A carbon nanotube film is obtained. Referring to Figures 2 to 4, in step (ai), a substrate 12 is provided, the substrate 12 having a surface 122. The substrate 12 is a flat circular substrate, the material of which is Glass, quartz, tantalum or alumina. This embodiment uses 4 inches Smoothing the base of the crucible. In step (a2), a catalyst layer 14 having two mutually parallel sides is formed on the surface 122 of the substrate 12. The method of forming the catalyst layer 14 includes a substrate treatment or a catalyst layer. The substrate processing method comprises: treating the surface 122 of the substrate 12, forming a separate growth surface having two mutually parallel sides on the surface 122 of the substrate 12; forming a growth surface of the substrate 12 Catalyst layer 14. The catalyst layer 098118658 Form No. A0101 Page 7 / 28 pages 0982031622-0 201043568 The processing method includes a template method, a photolithography method, etc. The template method includes the following steps: providing a mask, the mask And comprising a shielding portion and a hollow portion defined by the shielding portion, the hollow portion has two mutually parallel sides, and the catalyst layer 14 is formed on the surface 122 of the substrate 12 by the mask to make the catalyst layer 14 There are two mutually parallel sides. The photolithography method comprises the steps of: forming a catalyst layer 14 on the surface 122 of the substrate 12; The photolithographic treatment is performed so that the catalyst layer 14 has two mutually parallel sides, wherein the catalyst layer i 4 is defined by two mutually parallel sides and sides connecting the two sides. [00161 This embodiment adopts a template. The method is formed on the surface 12 2 of the substrate 12 to be formed - a catalyst layer 14 having two mutually parallel sides. Specifically, the template method comprises the steps of: first providing a mask 2 〇, the mask 2 〇 A masking portion 22 and a hollow portion 24 defined by the shielding portion 22 are included. The material of the reticle 20 is not limited as long as it does not deform during the subsequent process. The material of the enamel template 20 is preferably For metal materials. . . material. The reticle of the reticle 2 is divided into two sides which are parallel to each other. . . . 丨.. In the present embodiment, the material of the mask 20 is iron. The hollow portion 24 of the mask 20 has a rectangular shape. It is to be understood that the shape of the hollow portion 24 of the reticle 20 is not limited to the above embodiment, and may be other shapes having two mutually parallel sides, such as a "U" shape or other shapes. [0018] Next, the mask 20 is spaced from the substrate 12 such that the orthographic projection of the hollow portion 24 of the mask 20 completely falls on the substrate 12. The gap between the reticle 20 and the substrate 12 is greater than 0.1 mm and less than or equal to 100 mm. Preferably, the interval between the reticle 20 and the substrate 098118658 Form No. A0101, page 8 of 2882031622-0 201043568 12 is greater than 〇·1 millimeter and less than or equal to 丨〇mm. In the present embodiment, the interval between the mask 20 and the substrate 12 is 2 mm. [0019] Then, a catalyst layer 14 is formed on the substrate 12 by the hollow portion 24 of the mask 20, the catalyst layer 14 having two mutually parallel sides. Wherein the shape of the catalyst layer 14 corresponds to the shape of the hollow portion of the mask 20 . The catalyst layer 14 has a thickness of from 2 nm to 9 nm. The material of the catalyst layer 14 is an alloy of iron (Fe), cobalt (Co), nickel (Ni) or the like or any combination thereof. The method of forming the catalyst layer η includes an evaporation method, a thermal deposition method, an electron beam deposition method, or a sputtering method. In the present embodiment, the thickness of the catalyst layer 14 is from 3 nm to 6 nm. The material of the catalyst layer 14 is iron. The method of forming the catalyst layer η is an evaporation method. In the present embodiment, since the hollow portion 24 of the mask 2 has a rectangular shape, the catalyst layer 14 formed on the substrate 12 is also rectangular. [0020] Finally, 'removing the mask 2' [0021] In the step (a3), the substrate 12 having the catalyst layer 14 is annealed in high temperature air for about 30 minutes to 90 minutes to oxidize the catalyst layer 14 into The nano-scale catalyst particle layer with a relatively concentrated distribution of particles. [0022] In the step (a4), the annealed substrate 12 is placed in a reaction furnace, and heated to 7 Torr under a protective gas atmosphere (pCi1〇〇(rc, then a carbon source gas is reacted for a period of time) to obtain a a carbon nanotube array 1 . Since the carbon nanotube array 10 has at least two opposite parallel sides in a plane parallel to the surface 122 of the substrate 12 and a mutually parallel side of the catalyst layer 14 , The meter tube array 10 has a certain height, so the carbon nanotube array 098118658 Form No. A0101 Page 9 / Total 28 pages 0908231622-0 201043568 Column 10 has two substantially parallel sides 2 and sides 4, the side 2, the side 4 corresponding to two mutually parallel sides of the catalyst layer 14. The protective gas is an inert gas such as helium, neon, argon or helium. The carbon source gas is acetylene, ethylene or methane. In the present embodiment, the shielding gas is argon; the carbon source gas is acetylene; and the reaction for introducing the carbon source gas is 5 minutes to 30 minutes; the carbon nanotubes The height of the array is from 200 microns to 400 microns. The carbon nanotube array 10 is composed of a plurality of carbon nanotubes, and the plurality of carbon nanotubes are one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. In this embodiment, the plurality of carbon nanotubes are multi-walled carbon nanotubes, and the plurality of carbon nanotubes are substantially parallel to each other and perpendicular to the substrate 12, that is, the carbon nanotube array 10 is Super-aligned multi-walled carbon nanotube array. [0024] In this embodiment, since the shape of the catalyst layer 14 is a rectangle, the carbon nanotube array 10 includes oppositely disposed and substantially parallel sides 2 and Side 4, side 6 and side 8. By controlling the growth conditions, the carbon nanotube array 10 contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles, etc. [0025] in step (a5) First, a stretching tool 26 is provided to contact the carbon nanotubes in the carbon nanotube array 10 to form a contact surface, preferably, the contact surface and the nanocarbon The tube arrays 10 are perpendicular to and in contact with the two side faces 2, 4 of which are parallel to each other. wherein the stretching tool The length of 26 is greater than or equal to the vertical distance between the mutually parallel side 2 and the side 4 of the carbon nanotube array 10. In the embodiment, the stretching tool 26 is a tape, and the tape and the nanometer. Carbon tube array 10 connection 098118658 Form No. A0101 Page 10 / Total 28 page 0982031622-0 201043568 [0026] Ο ❹ [0027] [0028] 098118658 The plurality of carbon nanotubes at the contact are bonded to form a contact surface, and The length of the tape is slightly greater than the vertical distance between the mutually parallel sides 2 and 4 of the carbon nanotube array 10. Secondly, the nanocarbon camp array 10 is stretched in a direction substantially parallel to the two mutually parallel sides of the carbon nanotube array 1 and at a predetermined angle to the substrate 12, and the pulling The plurality of carbon nanotubes bonded by the stretching tool 26 are gradually separated from the substrate 12 in the stretching direction by the tensile force, and at the same time, due to the effect of the van der Waals force, the selected plurality of carbon nanotubes and the other non-meter carbon g are respectively Connected continuously and continuously. Since the distance between the two side faces 2 and the side faces 4 of the carbon nanotube array 10 which are parallel to each other is substantially the same ', thereby forming a continuous V-shaped carbon tube film 28 having the same width and regular shape. At the same time, the (four) carbon (four) 28 also has good continuity and uniformity. Wherein, the direction of the carbon nanotubes in the carbon nanotube film 28 is substantially parallel to the stretching direction of the carbon nanotube film. The range of the preview angle is greater than 〇. And less than or equal to 3 〇. Preferably, it is greater than 0 ' and less than or equal to 5. . The length of the carbon nanotube film 28 is not limited and can be obtained according to actual needs. ^米碳(四)(四)轮(四)Women's heart shape =. In the present embodiment, the stretching tool 26 is flush with the side 2 and the side 4 of the carbon nanotube row 10. The direction of the crucible is and the plurality of carbon nanotubes at the bond are stretched at 5° to the substrate 12. The second embodiment provides a method for preparing a carbon nanotube, which mainly includes the following steps: (b" providing a substrate, the surface of the substrate; (10), the surface of the substrate is formed with a form number of two^ a layer 7 of the side; (8)) annealing the substrate formed with the catalyst layer of 28 pages 0982021622-0 201043568 in high temperature air; (b4) placing the annealed substrate in the reaction furnace Heating in a protective atmosphere to 700 ° C to 100 (TC, then passing through a carbon source gas for a period of time, growing to obtain a carbon nanotube array 'The carbon nanotube array has two substantially parallel sides, the two a side surface corresponding to two mutually parallel sides of the catalyst layer; (b5) pulling a carbon nanotube from the carbon nanotube array in a direction parallel to the two sides to obtain a carbon nanotube The preparation method is basically the same as the method of the carbon nanotube film provided by the first embodiment, except that the specific steps of the step (b2) in the embodiment are the same as in the first embodiment. The specific steps of step (a2) of . . . are different [0029] [0030] 31] 098118658 Referring to FIG. 5 and FIG. 8 together, in step (bl), a substrate 32 is provided, and the substrate 32 has a surface 322. The material and shape of the substrate 32 are the same as those of the substrate 12 in the first embodiment. The material and shape are the same. In the step (b2), a surface of the substrate 32 is formed with two 34. The method for forming the catalyst layer 34 is a substrate treatment method. The substrate treatment method comprises the following steps: The surface 322 of the substrate 32 is treated to form a separate growth surface 320 having two mutually parallel sides on the surface 322 of the substrate 32. The growth surface 320 of the substrate 32 forms a catalyst layer 34. The method of forming the surface 322 of 32 into a separate growth surface 320 having two mutually parallel sides comprises: forming at least two mutually parallel recesses 324 'in two parallels on the substrate surface 322 by photolithography or laser method. The substrate surface 322 between the grooves 324 is a growth surface 320'. The growth surface 320 and the remaining surface 326 of the substrate surface 322 are separated by a groove 324. The shape of the substrate 32 shown in Fig. 6 is A0101 Page 12 of 28 0982031622-0 201043568 Formed by the method. The base 32 of the _6 is shaped such that the base surface 322 forms two pairs of mutually parallel grooves 324 through which the growth surface 320 is parallel to each other. The recess 324 is separated from the remaining surface 326, and the growth surface 320 is rectangular in shape. Alternatively, a portion of the remaining surface 326 of the substrate surface 322 may be removed by photolithography or laser to reduce the thickness of the remaining surface 326. Thin, a surface 322 of the substrate 32 forms a separate growth surface 320 having two mutually parallel sides. The shape of the substrate 32 shown in FIG. 7 is such that the shape of the substrate 32 in FIG. 7 formed by the square method is such that the thickness of the remaining surface 326 is reduced such that the rectangular growth surface 32 protrudes from the remaining surface. 326. The surface of the substrate 32 is independently formed by a fine-grained laser shirt to form a separate growth surface having two parallel sides. The shape of the substrate 32 shown in Fig. 8 is formed by this method. The growth surface 320 in Fig. 8 is rectangular and the base 32 has a rectangular parallelepiped shape.刚 In the present embodiment, a separate growth surface 320 is formed on the surface 322 of the substrate 32 by laser. Specifically, first, a laser is provided, and the illumination path of the laser beam of the laser can be controlled by a computer program. Next, the opening of the substrate 32 is input into the computer program to control the illumination path of the laser beam in the laser, and the growth surface 320 is formed on the surface 322 of the substrate 32. Then, the laser is turned on, the surface 322 of the substrate 32 is illuminated with a laser beam, and the laser beam is irradiated along the dotted line in FIG. 5 to the surface 322 of the substrate 32, and the remaining surface 326 of the substrate 32 is cut away. In part, the growth surface 320 is obtained such that the shape of the substrate 32 becomes long 0982031622-0 098118658 Form No. A0101 Page 13 / 28 pages 201043568 Square shape, as shown in FIG. It will be appreciated that by immobilizing the laser beam, the substrate 32 is moved such that the laser beam illuminates the surface 322 of the substrate 32, controlling the path of motion of the substrate 32, and ablating the substrate 32. [0035] It will be understood that the shape of the growth surface 320 is not limited to the second embodiment, and may be other shapes having two sides parallel to each other, such as a "U" shape or other shapes. [0036] In the step (b3), the substrate 32 on which the catalyst layer 34 is formed is annealed in high-temperature air for about 30 minutes to 90 minutes, and the catalyst layer 34 is oxidized to a nano-sized catalyst particle layer having a relatively large particle size distribution. . [0037] In the step (b4), the annealed substrate 32 is placed in a reaction furnace, heated to 700 to 1 000 ° C under a protective gas atmosphere, and then passed through a carbon source gas for a period of time to obtain a nanometer. Carbon tube array 30. The shielding gas, the carbon source gas, the reaction time of the carbon source gas, the height and shape of the carbon nanotube array 30 in the present embodiment are respectively reacted with the shielding gas, the carbon source gas, and the carbon source gas in the first embodiment. The carbon nanotube array 10 has the same height and shape. [0038] In the step (b5), a carbon nanotube film 38 is drawn from the carbon nanotube array 30 in a direction parallel to the two mutually parallel sides. The specific method of this step (b5) is the same as the specific method of the step (a5) of the first embodiment. The preparation method of the carbon nanotube film provided by the embodiment of the present invention has the following advantages: by processing the catalyst layer or the substrate, the carbon nanotube array in the preparation method has two mutually parallel sides, so Parallel to the side 098118658 Form No. A0101 Page 14 / Total 28 Page 0982031622-0 201043568 Pulling multiple nano skirts & in the direction of the face, you can get a good uniformity, the same width and the shape rule Water tube film. The method is simple and easy to use, and the cost is low, and the reading of the Qinmu tube film does not require subsequent processing, and can be directly applied in the industry, and is advantageous for mass production in the industry. [0040] In summary, the present invention has indeed applied for a patent application in accordance with the requirements of the invention patent. However, the above-mentioned acts are merely preferred embodiments of the present invention, which are not intended to limit the scope of the patent. Any equivalent modifications or variations made by those skilled in the art to the present invention in accordance with the present invention should be covered by the following claims. BRIEF DESCRIPTION OF THE DRAWINGS [11] A flow chart of a method for preparing a carbon nanotube film according to a first embodiment of the present invention. 2 is a side view of a substrate for growing a carbon nanotube array for producing a carbon nanotube film according to a first embodiment of the present invention. 3 is a plan view of a substrate for growing a carbon nanotube array for producing a carbon nanotube film according to a first embodiment of the present invention. 4 is a flow chart showing a process for preparing a carbon nanotube film according to a first embodiment of the present invention. 5 is a flow chart showing a process for preparing a carbon nanotube film according to a second embodiment of the present invention. 6, FIG. 7 and FIG. 8 are schematic diagrams showing the shape of a substrate having a growth surface according to an embodiment of the present invention. [Major component symbol description] 098118658 Form No. A0101 Page 15 of 28 0982031622-0 201043568 Side 2; 4; 6; 8 Carbon nanotube array 10; 30 Substrate 12; 32 Substrate surface 122; 322 Catalyst layer 14 34 Masking plate 20 Masking portion of masking plate 22 Hollow portion of masking plate 24 Stretching tool 26 Carbon nanotube film 28; 38 Growth surface 320 Groove 324 Remaining surface 32 6 ' 098118658 Form No. A0101 Page 16 of 28 Page 0982031622-0