201135797 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種透射電鏡微柵及其製備方法，尤其涉及 —種基於奈米碳管的透射電鏡微柵及其製備方法。 [0002] 【先前技術】 在透射電子顯微鏡中’多孔碳支持膜（微樹）係用於承 栽粉末樣品，進行透射電子顯微鏡高分辨像（HRTEM)觀 察的重要工具。隨著奈米材料研究的不斷發展，微栅在 ❹ [0003] 奈米材料的電子顯微學表徵領域的應用日益廣泛。 先前技術中，該應用於透射電子顯微鏡的微柵通常係在 銅網或鎳網等金屬網格上覆蓋一層多孔有機膜，再蒸鍍 —層非晶碳膜製成的。然而，當採用上述微柵對被測樣 品的透射電鏡高分辨像進行成份分析時，金屬網格因其 經常含有較多雜質，如金屬氧化物等，對被測樣品成份 分析的干擾較大。 [0004] 自九十年代初以來，以奈米碳管（請參見Helical microtubules of graphitic carbon, Nature, Sum-i〇 Iijima，v〇l 354，p56(1991 ))為代表的奈米材料 以其獨特的結構和性質引起了人們極大的關注。將奈米 碳管應用於微栅的製作，有利於降低金屬網格對被測樣 品成份分析的干擾。 [0005] 【發明内容】 有黎於此’提供一種基於奈米碳管的透射電鏡微柵及其 製備方法實為必要，該透射電鏡微柵對被測樣品成份分 析的干擾較小。 099110666 表單編號A0101 第3頁/共32頁 0992018762-0 201135797 [0006] [0007] [0008] [0009] [0010] 該透射電鏡微栅包括一純碳網格及至少一奈米碳管膜， 該純碟網格具有複數個網孔，所述至少一奈米碳管膜覆 蓋所述純碳網格的複數個網孔。 ~~種透射電鏡微栅的製備方法，包括以下步驟：提供一 純碟網格預製體；提供至少一奈米碳管膜，將至少一奈 米碳管膜鋪設在所述純碳網格預製體表面；以及按預定 尺寸切割所述純碳網格預製體及至少一奈米碳管膜，形 成所述透射電鏡微栅。 相較於先前技術，本發明提供的透射電鏡微柵包括一純 :....ν' .-- 蚊網格及至少一奈米碳管膜，無需I屬網格，且純碳網 格及至少一奈米碳管臈均較為純淨’可有效消除傳統微 柵中的金屬網格對被測樣品成份分析時的干擾，從而有 利於提高採用透射電鏡進行成份分析時的精確度。 【實施方式】 下面將結合附圖對本發明遷射電鏡微柙及其製備方法作 進一步的詳細說明。 請-併參閱m及圖3 ’本發明種透射電鏡微_ 。該透射電鏡微柵10包括一純碳網格1〇2及至少一奈米碳 管膜104。所述至少一奈米碳管膜1G4設置在該純碳:格反 102表面。所述純碳網格102及至少—奈米碳管膜ι〇4較 為純淨。所述純碳網格丨02可為圓片狀，直徑約為3毫米 所述純碳網格1G2為自支撐結構，且具有複數個網孔⑽ 。所述自支偉為純碳網格1{)2不需要大面積的載體支樓， 099110666 表單編號A0101 第4頁/共32頁 0992018762-0 [0011] 201135797 Ο 而只要相對兩邊提供支撐力即能整體上懸空而保持自身 片狀結構。所述至少一奈米碳管膜104覆蓋所述純碳網格 102的複數個網孔106。所述網孔106的形狀不限，依據 不同的製備方法，如採用雷射照射形成所述複數個網孔 106時，選擇不同形狀的雷射光束或採用不同的雷射照射 方式所形成的網孔106的形狀可為圓形、方形、橢圓形等 。所述網孔106的尺寸不限，可根據實際應用需求調整。 優選地，所述網孔106為圓形孔。所述網孔106可為通孔 ，即其可從純碳網格10 2的一個表面延伸至與該表面相對 的另一表面。所述網孔1 0 6的排列方式不限。所述網孔 106之間的距離可相等或不等。優選地，所述網孔106均 勻分佈在所述純碳網格102表面或所述複數個網孔106以 陣列形式分佈在所述純碳網格102表面，且相鄰的網孔 106之間的距離相等。相鄰的網孔106之間的距離可大於1 微米。所述純碳網格102的厚度可約為3~20微米。所述網 孔106的尺寸約為10微米〜200微米。所述純碳網格102的 材料可為炭黑或奈米碳管。 [0012] 當所述純碳網格102的材料為炭黑時，所述純碳網格102 即為一圓片狀炭黑膜。所述網孔106的尺寸優選為30微米 〜200微米。 [0013] 當所述純碳網格102的材料為奈米碳管時，所述純碳網格 102為一圓片狀奈米碳管結構。所述圓片狀奈米碳管結構 為一自支撐結構且具有一定的支撐性能。優選地，所述 圓片狀奈米碳管結構具有較好的支撐性能。所述自支撐 為圓片狀奈米碳管結構不需要大面積的載體支撐，而只 099110666 表單編號Α0101 第5頁/共32頁 0992018762-0 201135797 要相對兩邊提供支撐力即能整體上懸空而保持自身片狀 結構。所述圓片狀奈米碳管結構可包括至少一層奈米碳 管膜。組成圓片狀奈米碳管結構的奈米碳管膜的層數根 據單層奈米碳管膜的厚度而定，以所述圓片狀奈米碳管 結構具有較好的支撐性能為準。可以理解，單層奈米碳 管膜的厚度越小，所述圓片狀奈米碳管結構中奈米碳管 膜的層數越多；單層奈米碳管膜的厚度越大，所述圓片 狀奈米碳管結構中奈米碳管膜的層數越少。相鄰兩層奈 米碳管膜之間可通過凡德瓦爾力緊密結合。所述奈米碳 管膜可為奈米碳管絮化膜、奈米碳管碾壓膜或奈米碳管 拉膜。 [0014] 所述奈米碳管絮化膜包括複數個相互纏繞且均勻分佈的 奈米碳管。所述奈米碳管之間通過凡德瓦爾力相互吸引 、纏繞，形成網路狀結構，以形成一自支撐的奈米碳管 絮化膜，其掃描電鏡照片可參閱圖4。所述奈米碳管絮化 膜各向同性。所述奈米碳管絮化膜可通過對一奈米碳管 陣列絮化處理而獲得。所述奈米碳管絮化膜及其製備方 法請參見於2008年11月16日公開的第200844041號中華 民國公開專利申請。為節省篇幅，僅引用於此，但所述 申請中的所有技術揭露也應視為本發明申請技術揭露的 一部分。值得注意的係，所述奈米碳管絮化膜並不限於 上述製備方法。所述奈米碳管絮化膜的厚度為1微米至2 毫米。所述奈米碳管結構可僅包括一層奈米碳管絮化膜 ，通過調節其厚度來確保其具有較好的支撐性能。 [0015] 所述奈米碳管碾壓膜包括複數個奈米碳管無序排列、沿 099110666 表單編號A0101 第6頁/共32頁 0992018762-0 201135797 一個方向擇優取向排列或沿複數個方向擇優取向排列， 相鄰的奈米碳管通過凡德瓦爾力結合。該奈米碳管碾壓 膜可以通過採用一平面壓頭沿垂直於上述奈米碳管陣列 生長的基底的方向擠壓上述奈米碳管陣列而獲得，此時 所述奈米碳管碾壓膜中的奈米碳管無序排列，該奈米碳 管碾壓膜各向同性；所述奈米碳管碾壓膜也可以採用一 滾軸狀壓頭沿某一固定方向碾壓上述奈米碳管陣列而獲 得，此時所述奈米碳管碾壓膜中的奈米碳管在所述固定 方向擇優取向排列；所述奈米碳管碾壓膜還可以採用滾 Ο 軸狀壓頭沿不同方向碾壓上述奈米碳管陣列而獲得，此 時所述奈米碳管碾壓膜中的奈米碳管沿不同方向擇優取 向排列此時，所述奈米碳管碾壓膜可包括複數個部分， 每個部分中的奈米碳管沿一個方向擇優取向排列，且相 鄰兩個部分中的奈米碳管的排列方向可不同。所述奈米 碳管碾壓膜的掃描電鏡照片請參閱圖5。所述奈米碳管碾 壓膜及其製備方法請參見於2009年1月1曰公開的第 200900348號中華民國公開專利申請。為節省篇幅，僅 ◎ 引用於此，但所述申請中的所有技術揭露也應視為本發 明申請技術揭露的一部分。所述的奈米碳管碾壓膜的厚 度為1微米至1毫米。所述奈米碳管結構可僅包括一層奈 米碳管碾壓膜，通過調節其厚度來實現其具有較好的支 撐性能。 [0016] 請參見圖6，所述奈米碳管拉膜係由若干奈米碳管組成的 自支撐結構。所述若干奈米碳管沿同一方向擇優取向排 列。所述擇優取向係指在奈米碳管拉膜中大多數奈米碳 099110666 表單編號A0101 第7頁/共32頁 0992018762-0 201135797 管的整體延伸方向基本朝同—方向。而 ^碳管的整體延伸方向基本平行於奈米碳管拉膜的表 過凡Si地：所述奈米碳管拉膜中多數奈米碳管係通 臭心_力耳尾相連。具體地，所述奈米碳管拉膜中 基本朝同—方向延伸的大多數奈米碳管中每—太米碳管 方向亡相鄰的奈米碳管通過凡德瓦爾力編 田…、所述奈米碳管拉膜中存在少數隨機 些奈米碳管不會對奈米碳_大多數奈 :_二=顯影響。所述自奈 餘_靖，^只要相對兩邊 :#即能整體上懸空而保持自身膜狀狀態，即將 〜米破管拉膜置於（或固定於）間隔—定距離設置的 Z支撑體上時，位於兩個切體之_奈米碳管拉模 空簡自身難狀態。所述自支撐主要通過奈米 碳管拉臈中存在連續的通過凡德瓦爾力首尾相連延仲排 列的奈米碳管而實現。 [0017] 具體地’所述奈米碳管拉膜中基本朝同—方向延伸的多 數奈米碳管並㈣對的直線狀，可以適#”曲；或者 並非完全按照延伸方向上排列，可以適當的偏離延伸方 向。因此’不能排除奈米碳管拉膜的基本朝同一方向延 伸的多數奈米碳管中並列的奈米碳管之間可能存在部分 接觸。具體地’每-奈米碳管拉膜包括複數個連續且擇 優取向排列的奈米碳管片段。該複數個奈米碳管片段通 過凡德瓦爾力首尾相連。每—奈米碳管片段包括複數個 基本相互平行的奈料管’該複數個基本相互平行的奈 099110666 表單編號A0101 第8頁/共32頁 0992018762-0 201135797 ❹ [0018] 米碳管通過凡德瓦爾力緊密結合。該奈米碳管片段具有 任意的長度、厚度、均勻性及形狀。該奈米碳管拉膜中 的奈米碳管沿同一方向擇優取向排列。所述奈米碳管拉 膜為從一奈米碳管陣列中拉取獲得。根據奈米碳管陣列 中奈米碳管的高度與密度的不同，所述奈米碳管拉膜的 厚度為0.5奈米〜100微米。所述奈米碳管拉膜的寬度與拉 取該奈米碳管拉膜的奈米碳管陣列的尺寸有關，長度不 限。當所述奈米碳管膜的厚度為0. 5奈米〜100微米時，所 述奈米碳管結構可包括10層以上層疊設置的奈米碳管膜 。優選地，所述奈米碳管結構可包括100層以上層疊設置 的奈米碳管膜。 Ο 當圓片狀奈米碳管結構包括複數個奈米碳管膜且每個奈 米碳管膜中的奈米碳管沿同一方向擇優取向排列時，相 鄰兩層奈米碳管膜中的奈米碳管的排列方向可相同或不 同。具體地，相鄰的奈米碳管膜中的奈米碳管之間具有 一交叉角度α，且該α大於等於0度且小於等於90度。當 圓片狀奈米碳管結構中的複數個奈米碳管膜中的奈米碳 管之間具有一交叉角度α且α不等於0度時，即複數個奈 米碳管膜交叉設置時，所述奈米碳管相互交織形成一網 狀結構，使所述圓片狀奈米碳管結構的機械性能增強。 [0019] 可以理解，複數個奈米碳管膜交叉設置並不要求任意兩 層相鄰的奈米碳管膜均交叉設置，即允許存在相鄰兩層 奈米碳管膜中的多數奈米碳管的排列方向相同的情形， 但需確保圓片狀奈米碳管結構中存在至少兩層奈米碳管 膜中的多數奈米碳管的排列方向之間的交叉角度大於0度 099110666 表單編號Α0101 第9頁/共32頁 0992018762-0 201135797 且小於等於90度。 [0020] [0021] 099110666 本實施例中，所述純碳'網格1 〇 2為1 〇 〇層奈米*反官' 拉膜交 叉設置形成的具有自支撐結構的圓片狀奈米碳管結構。 相鄰兩層奈米碳管拉膜中的奈米碳管之間具有一交又角 度β，且該α等於9〇度。所述網孔1〇6為圓形孔，其孔徑 在30微米〜150微米之間。 所述至少一奈米碳管膜丨〇4覆蓋所述純碳網格1〇2中的複 數個網孔10 6。所述覆蓋網孔10 6的至少一奈米碳管膜 1 0 4在網孔處懸空設置。每個網孔處懸空設置的至少一奈 米碳管膜104對應為一個電子透射部。該寃子透射部用於 承載被測樣品用於透射電鏡觀察。所述至少一奈米碳管 膜104優選為奈米板營拉膜。當有兩層以上的奈米碳管拉 膜覆蓋所述複數個網孔時’該兩層以上的奈米碳管拉 膜優選為交叉設置。所述交叉設置的兩層以上的奈米碳 管拉膜之間的交叉角度優選為90赛。由於複數個奈米碳 管拉膜交叉設置’不同層奈米碳管拉臟中的奈米碳管之 間相互交織形成一網狀結構’使所述至少一奈米碳管膜 104的機械性能增強’同時使該至少一奈米碳管膜1〇4具 有複數個均勻且規則排布的微孔108，該微孔1〇8的孔徑 與奈米碳管膜的層數有關，層數越多，微孔108的孔徑越 小。所述微孔108的孔徑可為1奈米~·1微米。此外，該至 少一奈米碳管膜104的厚度優選小於1〇〇微米。本實施例 中，有兩層交叉5史置的奈米奴官膜拉膜覆蓋所述透射電 鏡微柵10中的複數個網孔。 由於本實施例中的透射電叙微橋1 0由純碳網格1 〇 2及至少 0992018762-0 表單煸號Α0101 第10頁/共32頁 [0022] 201135797 [0023] Ο 〇 一=碳管_組成，不含有金屬網格，且純碳網格 =至少一奈米碳管_為純淨，對被 =無干擾’因此，可有效消除傳統微栅中的金屬網格 子被測樣品成份分析日杨干擾，從而有利於提高透射電 鏡10進行成份分析時的精確度。 本實施例透射電鏡微栅H)在應用時，待觀察的材料樣。 承放在所述至少—奈米碳管㈣4表面。當所述材料= 的尺寸大於所述至少-奈米碳管膜1〇4的微孔1〇8時所 述微孔繼可以支援該材料樣品β可通過對應於網孔1〇6 的電子透射部Μ該麵樣品1當所述材料樣品的尺 寸小於所述微孔1G8時，尤其當所料料樣品為粒徑小於 5奈来的奈米顆粒時，所述材料樣品可通過至少一奈米碳 管膜104中的奈米碳管的吸附作用被穩定地吸附在奈求碳 管管壁表面，此時，亦可通過對應於網孔1〇6的電子透射 部觀測該材料樣品。從而，本發明的透射電鏡微拇1〇可 實現用於觀測粒徑小於5奈米的奈米顆粒材料樣品，從而 消除傳統微柵中的非晶碳蹲對粒徑小於5奈米的奈米顆粒 的透射電鏡高分辨像觀察的影響。 [0024] 請參閱圖7，本發明還提供上述透射電鏡微柵10的製備方 法，該方法包括以下步驟： [0025] 步驟一、提供一純碳網格預製體。 [0026] 當所述純碳網格預製體為月狀炭黑膜時，所述純碳網格 預製體的製備方法包括以下步驟： [0027] 首先，提供一碳漿料及一支撐體。 099110666 表單編號A0101 第11頁/共32頁 0992018762-0 201135797 [0028] [0029] 所述碳漿料可包括液體混合物及炭黑。其中，所述液體 混合物可佔所述碳漿料的品質百分含量為丨5_95% (即 15-95wt%)，所述炭黑可佔所述碳漿料的5_85忖％。所 述液體混合物可包括溶劑及黏度調節劑。所述溶劑可為 水、醇類或祐類化合物等。所述醇類可為甲醇、乙醇、 丙醇、丁醇、戊醇 '庚醇、乙二醇、丙二醇、丙三醇、 苯甲醇或烯丙醇等。所述萜類化合物為異冰片、冰片、 茨_、茨醇、茨院、薄荷_、薄荷醇或松油醇等。所述 冷劑的重量百分含量可為所述液體混合物的2〇_99. 。所述黏度調節劑可為澱粉或其鹽、纖維素或其鹽、或 聚趟類。所述纖維素或其鹽可為甲基纖維素乙基纖維 素、纖維素醋_魏甲基纖維素納n聚醚類為聚 乙二醇、聚丙二醇、聚丙三醇、或乙二醇和丙二醇的共 聚物等。所述黏度調節劑的重量百分含量可為所述液體 混合物的〇. 5-40 wt%。 .：： ；：： : 可選擇地，所述液體混合福可進―步包g一表面活性劑 或-黏合劑。該表祕性劑可輕氧_賴表面活性 劑如聚乙二醇辛基苯基醚（TritonX 1〇〇 )或辛基酚 聚氧乙烯醚（Trit〇nX405 )。該表面活性劑可佔所述液 t*。物的。σ質百分含量為〇. 5_2〇wt%。所述黏合劑的 添加量可為所述液體混合物的〇. 5-20wt9i^所述黏合劑 可為粉末二氧化錫或二氧化錫膠體。 所述奴漿料可通過將黏度調節劑溶於溶劑中，待混合均 勻後加入炭黑’然後進行機械挽掉而製備。所述機械攪 拌的時間約為3_6小時。本實施例中，可將〇. 2克乙基纖 099110666 表單編號A0101 第12頁/共32頁 0992018762-0 [0030] 201135797 [0031] 維素升異丙•中，並進行機械麟使其溫合对 句 約6克炭黑粉末’繼續機械攪拌約4小時， 衫成所述碳漿料。 戶斤述支Μ可料在製制財切所❿炭衆料。所述 支獲體的材料不限。職支賴可為_玻璃基板或〆陶 篆片。本實施例中’所述支额為—玻璃基板。 [0032] 其次，印刷所述碳漿料至所述支撐體。 [0033] ❹ 所述印刷錢料輯述支職的衫可祕網印刷法、 刮塗法、旋轉塗膜、滴膜或提拉法等方法。本實施例， 通過絲網印刷法印刷所述碳漿科至所述支撐體。 [0034] 再次’烘乾所述碳漿料，形成一純碳膜^可採取室溫下 自然晾乾或加熱法來烘乾所述碳漿料。 [0035] 最後，按照預定圖形對所述純碳膜進行打孔，並分離所 述純碳膜與支撐體，形成所述純碳網格預製體。 [0036] ❹ 對所述純碳膜進行打孔的方法包括雷射打孔法。具體地 ’對所述純碳膜進行打孔的方法包括以下步驟：提供〆 聚焦雷射光束；按照預定圖形逐點將所述聚焦雷射光柬 照射至所述純碳膜，從而形成複數個網孔106。該雷射光 束可通過傳統的氬離子雷射器或二氧化碳雷射器產生。 該雷射光束的功率為5〜30瓦（W)，優選為18W。具體地’ 099110666 可選擇脈衝雷射光束採用逐點掃描的方式實現照射純碟 媒形成複數個網孔106。所謂“間隔照射”即在對所述純 碳犋進行雷射打孔時，雷射光束為間歇式照射，且照射 至所述純碳膜的不同位置，該不同位置之間間隔一定距 表單蝙珑Α0101 第13頁/共32頁 099 201135797 離，以確保在所述純碳膜上形成複數個間隔設置的網孔 106。所述複數個網孔106成陣列分佈。所述網孔106的 形狀不限，可為圓形、方形或橢圓形等。本實施例中， 所述網孔1 0 6的形狀為圓形。 [0037] 當所述純碳網格預製體的材料為奈米碳管時，所述純碳 網格1 0 2的製備方法包括以下步驟： [0038] 首先，提供一片狀奈米碳管結構。 [0039] 所述片狀奈米碳管結構由至少一奈米碳管膜組成。所述 奈米碳管膜可為奈米碳管拉膜、奈米碳管碾壓膜或奈米 碳管絮化膜。本實施例中，所述片狀奈米碳管結構可通 過對複數個奈米碳管拉膜層疊且交叉設置而形成，該奈 米碳管拉膜為從一奈米碳管陣列中直接干法拉取獲得。 所述奈米碳管拉膜的製備方法包括以下步驟：提供一奈 米碳管陣列以及從上述奈米碳管陣列中抽取獲得至少一 具有一定寬度和長度的奈米碳管膜。 [0040] 所述奈米碳管陣列可為一超順排奈米碳管陣列。本實施 例中，所述奈米碳管陣列的製備方法採用化學氣相沈積 法，其具體步驟包括：（a)提供一平整基底，該基底可 選用P型或N型矽基底，或選用形成有氧化層的矽基底， 本實施例優選為採用4英寸的矽基底；（b)在基底表面 均勻形成一催化劑層，該催化劑層材料可選用鐵（Fe) 、鈷（Co)、鎳（Ni)或其任意組合的合金之一；（c) 將上述形成有催化劑層的基底在700〜900°C的空氣中退火 約30分鐘〜90分鐘；（d)將處理過的基底置於反應爐中 099110666 表單編號A0101 第14頁/共32頁 0992018762-0 201135797 ’在保護氣體環境下加熱到500〜74(TC，然後通入碳源氣 體反應約5〜30分鐘，生長得到超順排奈米碳管陣列，其 兩度為200〜400微米。該超順排奈米碳管陣列為複數個彼 此•平行且垂直於基底生長的奈米碳管形成的純奈米碳管 陣列°通過上述控制生長條件，該超順排奈米碳管陣列 中基本不含有雜質，如無定型碳或殘留的催化劑金屬顆 &等°該奈米碳管陣列中的奈米碳管彼此通過凡德瓦爾 力緊密接觸形成陣列。 [0041] Ο [0042] 本實施例中碳源氣可選用乙炔等化學性質較活潑的碳氫 化合物，保護氣體可選用氮氣、氦氣或惰性氣體。 771 —抵伸工具從奈米碳管陣列中拉取獲得奈米碳管膜 的步驟具體包括以下步驟：（a)從上述奈米碳管陣列中 〜定寬度的複數個奈米碳管片斷，本實施例優選為 田 曰 Ο [0043] 具有一定寬度的膠帶接觸奈米碳管離列以選定一定 寬度的複數個奈米碳管片斷；（b)以一定速度沿基本垂 直於奈米碳管陣列生長方向拉伸該複數個奈米碳管片斷 乂也成上述奈米碳管拉膜。201135797 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a TEM micro-gate and a preparation method thereof, and more particularly to a TEM-based TEM micro-grid and a preparation method thereof. [Prior Art] In a transmission electron microscope, a porous carbon support membrane (microtree) is an important tool for carrying a powder sample and performing transmission electron microscopy high resolution image (HRTEM) observation. With the continuous development of nanomaterial research, microgrids are increasingly used in the field of electron microscopy of ❹ [0003] nanomaterials. In the prior art, the microgrid applied to a transmission electron microscope is usually formed by covering a metal mesh such as a copper mesh or a nickel mesh with a porous organic film and then vapor-depositing a layer of amorphous carbon film. However, when the above-mentioned micro-gate is used to analyze the composition of the TEM high-resolution image of the sample to be tested, the metal mesh often contains a large amount of impurities, such as metal oxides, and the interference of the component analysis of the sample to be tested is large. [0004] Since the early 1990s, nanomaterials represented by carbon nanotubes (see Helical microtubules of graphitic carbon, Nature, Sum-i〇Iijima, v〇l 354, p56 (1991)) The unique structure and nature have aroused great concern. The application of nano carbon tubes to the fabrication of microgrids is beneficial to reduce the interference of metal grids on the analysis of the components of the sample being tested. [0005] SUMMARY OF THE INVENTION It is necessary to provide a TEM micro-gate based on a carbon nanotube and a preparation method thereof. The TEM micro-gate has less interference to the analysis of the sample component to be tested. 099110666 Form No. A0101 Page 3 / Total 32 Page 0992018762-0 201135797 [0007] [0009] [0010] The TEM microgrid includes a pure carbon grid and at least one carbon nanotube film, The pure dish mesh has a plurality of meshes, and the at least one carbon nanotube film covers a plurality of meshes of the pure carbon mesh. ~~ A method for preparing a transmission electron microstrip, comprising the steps of: providing a pure dish mesh preform; providing at least one carbon nanotube film, laying at least one carbon nanotube film on the pure carbon mesh prefabrication a surface of the body; and cutting the pure carbon mesh preform and the at least one carbon nanotube film to a predetermined size to form the TEM microgrid. Compared with the prior art, the TEM microgrid provided by the present invention comprises a pure: ....v'.-- mosquito net and at least one carbon nanotube film, without I-genus mesh, and pure carbon grid And at least one carbon nanotube is relatively pure' can effectively eliminate the interference of the metal grid in the traditional micro-grid on the analysis of the components of the sample to be tested, thereby improving the accuracy of component analysis using TEM. [Embodiment] Hereinafter, the present invention will be further described in detail with reference to the accompanying drawings. Please - see m and Figure 3 'the TEM of the invention. The TEM microgrid 10 includes a pure carbon grid 1〇2 and at least one carbon nanotube film 104. The at least one carbon nanotube film 1G4 is disposed on the surface of the pure carbon: lattice 102. The pure carbon grid 102 and at least the carbon nanotube membrane ι 4 are relatively pure. The pure carbon grid 丨 02 may be in the form of a disk having a diameter of about 3 mm. The pure carbon grid 1G2 is a self-supporting structure and has a plurality of meshes (10). The self-supporting weiwei is a pure carbon grid 1{) 2 does not require a large-area carrier branch, 099110666 Form No. A0101 Page 4 / Total 32 Page 0992018762-0 [0011] 201135797 Ο As long as the support is provided on both sides It can be suspended as a whole to maintain its own sheet structure. The at least one carbon nanotube film 104 covers a plurality of cells 106 of the pure carbon grid 102. The shape of the mesh 106 is not limited. When the plurality of meshes 106 are formed by laser irradiation according to different preparation methods, laser beams of different shapes or nets formed by different laser irradiation modes are selected. The shape of the holes 106 may be circular, square, elliptical, or the like. The size of the mesh 106 is not limited and can be adjusted according to actual application requirements. Preferably, the mesh 106 is a circular aperture. The mesh 106 can be a through hole, i.e., it can extend from one surface of the pure carbon grid 10 2 to another surface opposite the surface. The arrangement of the cells 1 0 6 is not limited. The distance between the cells 106 can be equal or unequal. Preferably, the mesh 106 is evenly distributed on the surface of the pure carbon mesh 102 or the plurality of meshes 106 are distributed in an array on the surface of the pure carbon mesh 102, and between adjacent meshes 106 The distance is equal. The distance between adjacent cells 106 can be greater than 1 micron. The pure carbon grid 102 can have a thickness of about 3 to 20 microns. The mesh 106 has a size of from about 10 microns to about 200 microns. The material of the pure carbon grid 102 may be carbon black or a carbon nanotube. [0012] When the material of the pure carbon grid 102 is carbon black, the pure carbon grid 102 is a disk-shaped carbon black film. The mesh 106 preferably has a size of from 30 micrometers to 200 micrometers. [0013] When the material of the pure carbon grid 102 is a carbon nanotube, the pure carbon grid 102 is a disk-shaped carbon nanotube structure. The disk-shaped carbon nanotube structure is a self-supporting structure and has certain supporting properties. Preferably, the disk-shaped carbon nanotube structure has better support properties. The self-supporting disk-shaped carbon nanotube structure does not require a large-area carrier support, but only 099110666 Form No. 1010101 Page 5 / Total 32 Page 0992018762-0 201135797 To provide support force on both sides, the whole can be suspended Keep your own sheet structure. The disk-shaped carbon nanotube structure may include at least one layer of carbon nanotube film. The number of layers of the carbon nanotube film constituting the disk-shaped carbon nanotube structure is determined according to the thickness of the single-layer carbon nanotube film, and the wafer-shaped carbon nanotube structure has good support performance. . It can be understood that the smaller the thickness of the single-layer carbon nanotube film, the more the number of layers of the carbon nanotube film in the disk-shaped carbon nanotube structure; the greater the thickness of the single-layer carbon nanotube film, The fewer the number of layers of the carbon nanotube film in the disk-shaped carbon nanotube structure. The adjacent two layers of carbon nanotube membranes can be tightly bonded by van der Waals force. The carbon nanotube membrane may be a carbon nanotube membrane, a carbon nanotube membrane or a carbon nanotube membrane. [0014] The carbon nanotube flocculation membrane comprises a plurality of carbon nanotubes which are intertwined and uniformly distributed. The carbon nanotubes are attracted to each other and entangled by van der Waals force to form a network structure to form a self-supporting carbon nanotube flocculation film. The scanning electron microscope photograph can be referred to FIG. The carbon nanotube film is isotropic. The carbon nanotube flocculation membrane can be obtained by flocculation treatment on a carbon nanotube array. The carbon nanotube flocculation membrane and the preparation method thereof are described in the Chinese Patent Application No. 200844041 published on November 16, 2008. To save space, reference is made only to this, but all of the technical disclosures in the application are also considered to be part of the disclosure of the present application. It is to be noted that the carbon nanotube flocculation film is not limited to the above production method. The carbon nanotube film has a thickness of from 1 micrometer to 2 millimeters. The carbon nanotube structure may include only one layer of carbon nanotube flocculation membrane, and its thickness is ensured to ensure better support performance. [0015] The carbon nanotube rolled film comprises a plurality of carbon nanotubes disorderly arranged along 099110666 Form No. A0101 Page 6 / Total 32 Page 0992018762-0 201135797 One direction preferred orientation or a plurality of directions Oriented, adjacent carbon nanotubes are combined by van der Waals force. The carbon nanotube rolled film can be obtained by extruding the carbon nanotube array in a direction perpendicular to the substrate grown by the array of carbon nanotubes by using a planar indenter, and the carbon nanotube is rolled at this time. The carbon nanotubes in the membrane are disorderly arranged, and the carbon nanotube membrane is isotropic; the carbon nanotube membrane can also be rolled in a fixed direction by a roller-shaped indenter. Obtained by a carbon nanotube array, wherein the carbon nanotubes in the carbon nanotube rolled film are arranged in a preferred orientation in the fixed direction; the carbon nanotube rolled film may also be rolled in a shaft shape The head is obtained by rolling the above-mentioned carbon nanotube array in different directions. At this time, the carbon nanotubes in the carbon nanotube rolled film are aligned in different directions. At this time, the carbon nanotube rolled film A plurality of sections may be included, the carbon nanotubes in each section being arranged in a preferred orientation in one direction, and the arrangement of the carbon nanotubes in the adjacent two sections may be different. See Figure 5 for a scanning electron micrograph of the carbon nanotube rolled film. The carbon nanotube rolled film and its preparation method are described in the Chinese Patent Publication No. 200900348 published on January 1, 2009. In order to save space, only ◎ is cited herein, but all technical disclosures in the application are also considered as part of the technical disclosure of the present application. The carbon nanotube rolled film has a thickness of from 1 μm to 1 mm. The carbon nanotube structure may include only one layer of carbon nanotube rolled film, and its thickness is adjusted to achieve better support performance. [0016] Referring to FIG. 6, the carbon nanotube film is a self-supporting structure composed of a plurality of carbon nanotubes. The plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. The preferred orientation refers to the majority of nanocarbons in the carbon nanotube film. 099110666 Form No. A0101 Page 7 / Total 32 Page 0992018762-0 201135797 The overall extension direction of the tube is substantially the same direction. And the overall extension direction of the carbon tube is substantially parallel to the surface of the carbon nanotube film. Si: The majority of the carbon nanotubes in the carbon nanotube film are connected to the odor heart. Specifically, in the carbon nanotube film, most of the carbon nanotubes extending substantially in the same direction extend adjacent carbon nanotubes in the direction of the carbon nanotubes, and the carbon nanotubes are adjacent to each other through the van der Waals force... There are a few random carbon nanotubes in the carbon nanotube film that do not affect the nanocarbon _ most na: _ two = significant. The self-contained _ jing, ^ as long as the two sides: # can be suspended as a whole to maintain its own membranous state, that is, the ~ meter broken tube is placed (or fixed) on the Z-support with a fixed distance At the time, the two carbon nanotubes are in a difficult state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the nano-carbon tube pulling through the van der Waals force. [0017] Specifically, the plurality of carbon nanotubes extending substantially in the same direction in the carbon nanotube film may be in a straight line, or may be arranged in a direction of extension. Appropriate deviation from the direction of extension. Therefore, there may be some contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes that extend substantially in the same direction of the carbon nanotube film. Specifically, 'per-nano carbon The tubular membrane comprises a plurality of continuous and preferentially oriented carbon nanotube segments. The plurality of carbon nanotube segments are connected end to end by van der Waals force. Each of the carbon nanotube segments comprises a plurality of substantially parallel materials. Tube 'The plurality of substantially parallel to each other 099110666 Form No. A0101 Page 8 / Total 32 Page 0992018762-0 201135797 ❹ [0018] The carbon tube is tightly coupled by Van der Waals force. The carbon nanotube segment has an arbitrary length , thickness, uniformity and shape. The carbon nanotubes in the carbon nanotube film are arranged in a preferred orientation in the same direction. The carbon nanotube film is drawn from an array of carbon nanotubes. According to the height and density of the carbon nanotubes in the carbon nanotube array, the thickness of the carbon nanotube film is 0.5 nm to 100 μm. The width of the carbon nanotube film is pulled and pulled. The size of the carbon nanotube array of the carbon nanotube film is not limited in length. When the thickness of the carbon nanotube film is 0.5 nm to 100 μm, the carbon nanotube structure may include Preferably, the carbon nanotube structure may include a carbon nanotube film stacked in a layer of 100 or more layers. Ο When the disk-shaped carbon nanotube structure includes a plurality of nanotubes When the carbon nanotube film and the carbon nanotubes in each carbon nanotube film are aligned in the same direction, the arrangement directions of the carbon nanotubes in the adjacent two layers of carbon nanotube film may be the same or different. Ground, the carbon nanotubes in the adjacent carbon nanotube film have an angle of intersection α, and the α is greater than or equal to 0 degrees and less than or equal to 90 degrees. When the plurality of wafer-shaped carbon nanotube structures When the carbon nanotubes in the carbon nanotube film have an intersection angle α and α is not equal to 0 degrees, that is, a plurality of nanocarbons When the membranes are disposed at the intersection, the carbon nanotubes are interwoven to form a network structure, which enhances the mechanical properties of the wafer-shaped carbon nanotube structure. [0019] It can be understood that a plurality of carbon nanotube membrane cross-settings are provided. It is not required that any two adjacent carbon nanotube films are cross-arranged, that is, the arrangement of the majority of the carbon nanotubes in the adjacent two layers of carbon nanotubes is allowed to be the same, but it is necessary to ensure the shape of the wafer. The intersection angle between the arrangement directions of the majority of the carbon nanotubes in the carbon nanotube structure is greater than 0 degrees 099110666 Form No. Α0101 Page 9 / Total 32 Page 0992018762-0 201135797 and less than [0020] In the present embodiment, the pure carbon 'grid 1 〇 2 is a wafer having a self-supporting structure formed by a cross-section of a layer of nano-reverses. Shaped carbon nanotube structure. The carbon nanotubes in the adjacent two layers of carbon nanotubes have an angle of intersection β between the carbon nanotubes, and the α is equal to 9 degrees. The mesh 1〇6 is a circular hole having a pore diameter of between 30 μm and 150 μm. The at least one carbon nanotube membrane 4 covers a plurality of cells 106 in the pure carbon grid 1〇2. The at least one carbon nanotube film 104 of the cover mesh 106 is suspended at the mesh. At least one carbon nanotube film 104 suspended at each of the meshes corresponds to an electron transmissive portion. The forceps transmission portion is used to carry the sample to be tested for transmission electron microscope observation. The at least one carbon nanotube film 104 is preferably a nanosheet film. When there are two or more layers of carbon nanotube film covering the plurality of cells, the two or more layers of the carbon nanotube film are preferably arranged in a cross. The crossing angle between the two or more layers of the carbon nanotube film which are disposed at the intersection is preferably 90 races. The mechanical properties of the at least one carbon nanotube film 104 are made due to the intersection of a plurality of carbon nanotube films and the intertwining of the carbon nanotubes in the different layers of carbon nanotubes to form a network structure. Enhancing 'at the same time, the at least one carbon nanotube film 1〇4 has a plurality of uniform and regularly arranged micropores 108, and the pore diameter of the micropores 1〇8 is related to the number of layers of the carbon nanotube film, and the number of layers is increased. More, the pore size of the micropores 108 is smaller. The pores 108 may have a pore size of from 1 nm to 1 μm. Further, the thickness of the at least one carbon nanotube film 104 is preferably less than 1 〇〇 micrometer. In this embodiment, a two-layered five-layered nanofilm film is used to cover a plurality of meshes in the transmission micromirror 10. Since the transmission electric microbridge 10 in this embodiment is made of pure carbon grid 1 〇 2 and at least 0992018762-0 form Α Α 0101 page 10 / total 32 pages [0022] 201135797 [0023] 〇 〇 1 = carbon tube _ composition, does not contain metal mesh, and pure carbon grid = at least one carbon nanotube _ is pure, the pair is = no interference' Therefore, it can effectively eliminate the sample analysis day of the metal grid in the traditional micro-grid The interference of the yang facilitates the improvement of the accuracy of the composition analysis of the TEM 10. In this embodiment, the TEM micro-gate H) is a material to be observed when applied. Placed on the surface of the at least-nanocarbon tube (four) 4. When the size of the material = is larger than the pores 1〇8 of the at least-carbon nanotube film 1〇4, the micropores can further support the material sample β to pass electron transmission corresponding to the mesh 1〇6 When the size of the material sample is smaller than the microporous 1G8, especially when the material sample is a nanoparticle having a particle diameter of less than 5 nanometers, the material sample can pass at least one nanometer. The adsorption of the carbon nanotubes in the carbon tube film 104 is stably adsorbed on the surface of the carbon tube wall, and at this time, the material sample can also be observed through the electron-transmissive portion corresponding to the mesh 1〇6. Therefore, the TEM micro-bend 1 of the present invention can be used for observing a sample of nano-particle material having a particle diameter of less than 5 nm, thereby eliminating the amorphous carbon 中 in the conventional micro-gate and having a particle diameter of less than 5 nm. The effect of high-resolution image observation of TEM on TEM. Referring to FIG. 7, the present invention further provides a method for preparing the above TEM micro-gate 10, the method comprising the following steps: [0025] Step 1: Providing a pure carbon mesh preform. [0026] When the pure carbon mesh preform is a moon carbon black film, the method for preparing the pure carbon mesh preform includes the following steps: [0027] First, a carbon slurry and a support are provided. 099110666 Form No. A0101 Page 11 of 32 0992018762-0 201135797 [0029] The carbon paste may include a liquid mixture and carbon black. Wherein, the liquid mixture may constitute 品质5_95% (i.e., 15-95% by weight) of the carbon paste, and the carbon black may account for 5_85% of the carbon paste. The liquid mixture can include a solvent and a viscosity modifier. The solvent may be water, an alcohol or a compound or the like. The alcohol may be methanol, ethanol, propanol, butanol, pentanol, heptanol, ethylene glycol, propylene glycol, glycerol, benzyl alcohol or allyl alcohol. The terpenoids are isobornyls, borneol, benzyl alcohol, ketamine, peppermint, menthol or terpineol. The weight percentage of the refrigerant may be 2〇_99. of the liquid mixture. The viscosity modifier may be starch or a salt thereof, cellulose or a salt thereof, or a polyfluorene. The cellulose or a salt thereof may be methyl cellulose ethyl cellulose, cellulose vinegar - Wei methyl cellulose nano n polyether is polyethylene glycol, polypropylene glycol, polyglycerol, or copolymerization of ethylene glycol and propylene glycol Things and so on. The weight percent of the viscosity modifier may be from 5% to 5-40% by weight of the liquid mixture. .:: ;:: : Alternatively, the liquid may be mixed with a surfactant or a binder. The secret agent can be light oxygen-based surfactant such as polyethylene glycol octylphenyl ether (TritonX 1〇〇) or octylphenol polyoxyethylene ether (Trit〇nX405). The surfactant can comprise the liquid t*. Physical. The percentage of σ mass is 〇. 5_2〇wt%. The binder may be added in an amount of 液体. 5-20wt9i^ The binder may be a powder of tin dioxide or a tin dioxide colloid. The slave slurry can be prepared by dissolving the viscosity modifier in a solvent, adding the carbon black after being uniformly mixed, and then mechanically pulling it off. The mechanical agitation time is about 3-6 hours. In this embodiment, 〇. 2g ethyl fiber 099110666 Form No. A0101 Page 12 / Total 32 Page 0992018762-0 [0030] 201135797 [0031] Wei Su Sheng isopropyl medium, and mechanical lining to make it warm Approximately 6 grams of carbon black powder was mixed and the mechanical stirring was continued for about 4 hours to form the carbon slurry. The accounts of the households can be expected to be used in the production of financial resources. The material of the support is not limited. The responsibilities can be _glass substrate or enamel enamel. In the present embodiment, the stated amount is a glass substrate. [0032] Next, the carbon paste is printed to the support. [0033] ❹ The printed money material describes a method of supporting a shirt, a screen printing method, a knife coating method, a spin coating film, a drip film or a pulling method. In this embodiment, the carbon paste is printed to the support by a screen printing method. [0034] The carbon slurry is again dried to form a pure carbon film. The carbon slurry can be dried by natural air drying or heating at room temperature. Finally, the pure carbon film is perforated according to a predetermined pattern, and the pure carbon film and the support are separated to form the pure carbon mesh preform. [0036] A method of perforating the pure carbon film includes a laser perforation method. Specifically, the method for perforating the pure carbon film includes the steps of: providing a 〆 focused laser beam; irradiating the focused laser light to the pure carbon film point by point according to a predetermined pattern, thereby forming a plurality of meshes 106. The laser beam can be generated by a conventional argon ion laser or carbon dioxide laser. The laser beam has a power of 5 to 30 watts (W), preferably 18 watts. Specifically, the '099110666' selectable pulsed laser beam is formed by spot-scanning to form a plurality of cells 106 by irradiating the pure disk. The so-called "interval illumination" means that when the pure carbon germanium is laser-perforated, the laser beam is intermittently irradiated and irradiated to different positions of the pure carbon film, and the different positions are spaced apart from each other by a form bat.珑Α0101 Page 13 of 32 099 201135797, to ensure that a plurality of spaced-apart meshes 106 are formed on the pure carbon film. The plurality of cells 106 are distributed in an array. The shape of the mesh 106 is not limited and may be circular, square or elliptical. In this embodiment, the shape of the mesh 106 is circular. [0037] When the material of the pure carbon mesh preform is a carbon nanotube, the preparation method of the pure carbon grid 1 0 2 includes the following steps: [0038] First, a piece of carbon nanotube is provided structure. [0039] The sheet-like carbon nanotube structure is composed of at least one carbon nanotube film. The carbon nanotube film may be a carbon nanotube film, a carbon nanotube film or a carbon nanotube film. In this embodiment, the sheet-shaped carbon nanotube structure can be formed by laminating and cross-setting a plurality of carbon nanotube films, which are directly dried from a carbon nanotube array. Fara takes it. The method for preparing the carbon nanotube film comprises the steps of: providing a carbon nanotube array and extracting at least one carbon nanotube film having a certain width and length from the carbon nanotube array. [0040] The carbon nanotube array can be a super-sequential carbon nanotube array. In this embodiment, the method for preparing the carbon nanotube array adopts a chemical vapor deposition method, and the specific steps thereof include: (a) providing a flat substrate, the substrate may be selected from a P-type or N-type germanium substrate, or may be formed. The ruthenium substrate having an oxide layer is preferably a 4-inch ruthenium substrate in this embodiment; (b) a catalyst layer is uniformly formed on the surface of the substrate, and the catalyst layer material may be selected from iron (Fe), cobalt (Co), and nickel (Ni). Or one of alloys of any combination thereof; (c) annealing the substrate on which the catalyst layer is formed in air at 700 to 900 ° C for about 30 minutes to 90 minutes; (d) placing the treated substrate in a reaction furnace Medium 099110666 Form No. A0101 Page 14 / Total 32 Page 0992018762-0 201135797 'In a protective gas atmosphere, heat to 500~74 (TC, then pass into the carbon source gas to react for about 5~30 minutes, grow to get super-shunned nanometer The carbon tube array is 200-400 micrometers twice. The super-sequential carbon nanotube array is a plurality of pure carbon nanotube arrays formed by carbon nanotubes which are parallel to each other and grow perpendicular to the substrate. Growth condition, the super-shunning nano The tube array contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles and the like. The carbon nanotubes in the carbon nanotube array are in close contact with each other to form an array by van der Waals force. [0041] Ο [ 0042] In the present embodiment, the carbon source gas may be a chemically active hydrocarbon such as acetylene, and the protective gas may be nitrogen, helium or an inert gas. 771 - The tensile tool is pulled from the carbon nanotube array to obtain the naphthalene The step of the carbon nanotube film specifically includes the following steps: (a) a plurality of carbon nanotube segments having a width from the carbon nanotube array, and the embodiment is preferably a field [0043] tape having a certain width. Contacting the carbon nanotubes to separate a plurality of carbon nanotube segments of a certain width; (b) stretching the plurality of carbon nanotube segments at a constant speed along a growth direction substantially perpendicular to the carbon nanotube array growth direction The above carbon nanotube film is pulled.
：： !L 在上述拉伸過程中，該複數個奈米碳管片斷在拉力作用 0拉伸方向逐漸脫離基底的同時，由於凡德瓦爾力作 用，該選定的複數個奈米碳管片斷分別與其他奈米碳管 片斷首尾相連地連續地被拉出，從而形成—奈米碳管拉 膜。转米碳官拉膜為基本沿拉伸方向排列的複數個奈 米碳管片斷首尾相連形成的具有—定寬度的奈米碳管膜 。該奈米碳管㈣的寬度與奈米碳管陣列所生長的基底 的尺寸有關’該奈米碳管拉膜的長度不限，可根據實際 099110666 表單編號Α0101 第頁/共32頁 0992018762-0 201135797 [0044] [0045] [0046] [0047] [0048] [0049] [0050] 需求制得。 所述層疊且交叉設置複數個奈米碳管拉膜的步驟可具體 包括以下步驟： 首先’提供一基體。該基底具有一平整表面，其材料不 限。本實施例中，該基底可為一陶瓷片。 其次，將上述奈米碳管拉膜依次層疊且交叉鋪設在所述 基體表面。 由於奈米碳管較為純淨且具有較大的比表面積，故從奈 米碳管陣列直接拉取也得的奈米複管也膜具有較好的黏 性。所述奈米碳管拉膜可直接鋪設在基體表面或另一奈 米碳管拉膜表面。所謂層疊立交叉設置即在層疊設置的 奈米碳管拉膜中，複數個奈米碳管拉膜中的奈米碳管之 間具有一交叉角度α且α不等於〇度。相鄰兩層奈米碳官 拉膜之間通過凡德瓦爾力緊密結合。 再次，對所述片狀奈米碳管結缚進行雷射打孔以形成複 數個網孔106 ° 本實施例中，所述複數個網孔1 〇 6的形成方式可具體包括 以下步驟： 提供一聚焦雷射光束’將所述聚焦雷射光束按照預定圖 形逐行逐點照射至所述片狀奈米碳管結構，雷射光束照 射位置處的>5狀奈米碳管結構中的奈米碳管被燒蝕，從 而形成複數個網孔1 。所述複數個網孔1〇6成陣列分佈 。所述網孔的形狀不限’可為圓形、方形或橢圓形等 099110666 表單編號Α0101 第16頁/共32頁 0992018762-0 201135797 [0051] [0052] Ο [0053] [0054] Ο 。本實施例中，所述網孔1 0 6的形狀為圓形。該雷射光束 可通過傳統的氬離子雷射器或二氧化碳雷射器產生。該 雷射光束的功率為5〜30瓦（W)，優選為18W。 具體地，可選擇脈衝雷射光束按照預定圖形採用逐行逐 點掃描的方式實現照射片狀奈米碳管結構的表面形成複 數個網孔106。所述複數個網孔106可成陣列分佈。具體 地，可採用下述兩種方式來實現： 方法一：固定所述片狀奈米碳管結構，移動雷射光束， 按照預定圖形使雷射光束間隔照射至所述片狀奈米碳管 結構表面。 方法二：固定雷射光束，移動所述片狀奈米碳管結構， 按照預定圖形使雷射光束間隔照射至所述片狀奈米碳管 結構表面。 可以理解，上述移動及照射步驟均可通過電腦程式控制 。所謂“間隔照射”即在對所述片狀奈米碳管結構進行 雷射打孔時，雷射光束為間歇式照射，且照射至所述片 狀奈米碳管結構的不同位置，該不同位置之間間隔一定 距離，以確保在所述片狀奈米碳管結構上形成複數個間 隔設置的網孔1 0 6。所述網孔10 6成陣列分佈。所述網孔 106可為通孔，即網孔106中可無奈米碳管殘留。可以理 解，所述網孔106中也可殘留有部分奈米碳管，該部分奈 米碳管同樣可用於支撐被測樣品。 步驟二、提供至少一奈米碳管膜104，將至少一奈米碳管 膜104鋪設在所述純碳網格102表面。 099110666 表單編號Α0101 第17頁/共32頁 0992018762-0 [0055] 201135797 [0056]所述至少—奈米礙管膜1〇4優選為奈米碳管拉膜，該奈米 碳管拉膜的製備方法與組成所述片狀奈米碳管結構的奈 米碳管拉膜的製備方法相同。 [0057] 由於奈米碳管較為純淨且具有較大的比表面積，故從奈 米碳管陣列直接拉取獲得的奈米碳管拉膜具有較好的黏 f生所述奈米峡管拉膜可直接鋪設在所述純礙網格1 〇 2表 面或另一奈米碳管膜表面。當有複數個奈米碳管拉膜鋪 設在所述純碳網格102表面時，該複數個奈米碳管拉膜可 依次層疊交叉鋪設在所述純碳網格102表面。相鄰兩層奈 米碳管拉膜之間通過凡德瓦爾力緊密結合。 [0058] 本實施例中，將四層奈米碳管拉'膜依次層疊並交又設置 在所述純碳網格102表面。相鄰兩層奈米碳管拉膜中的卉 米碳管之間的夾角為90度。該四層奈米碳管拉膜具有複 數個微孔108。該微孔1〇8的孔徑可為1奈米〜丨微米。 [0059] 進一步地，可使用有機溶劑處理該至少—奈米碳管膜1〇4 和純碳網格102。該有機溶劑為常溫下易揮發的有機溶劑 ，可選用乙醇、甲醇、丙酮、土氣乙烷和氣仿中一種或 者幾種的混合，本實施例中的有機溶劑採用乙醇。該有 機溶劑應與該奈米碳管具有較好的潤濕性。該使用有機 溶劑處理的步驟具體為：通過試管將有機溶劑滴落在至 少一奈米碳管膜104和純碳網格102表面，或者，也可將 上述至少一奈米碳管膜104和純碳網格1〇2浸入盛有有機 溶劑的容器中浸潤。有機溶劑處理後，由奈米碳管組成 的純碳網格102並排且相鄰的奈米碳管會聚攏，所述純碳 網格102具有較好的機械強度。所述至少一奈米碳管膜 099110666 表單編號A0101 第18頁/共32頁 0992018762-0 201135797 Ο 104經有機溶劑處理後，部分相鄰的奈米碳管會聚集形成 奈米碳管束。由於相鄰兩層奈米碳管膳中的奈米碳管具 有父又角度《 ’且0<〇：S90。，有機溶劑處理後的至少 ’τ'米奴管膜1 〇 4中的奈米碳管束相立交叉，從而形成複 數個微孔108。本該微孔1〇8的尺寸小於1〇微米，優選地 ，小於1微米。可以理解，該層疊在該純碳網格1〇2上的 至少一奈米碳管膜104的數量越多，所述微孔1〇8的尺寸 越小。因此，可通過調整該奈米碳管膜的數量得到需要 的微孔108尺寸。進一步地，通過有機溶劑處理還可使用 該至少一奈米碳管膜104與純碳網格102結合緊密，從而 使該至少一奈米碳管膜丨〇4更牢固她固定在該純碳網格 102 上。 [0060] [0061] 〇 步驟三、按預定尺寸切割所述至少一奈米碳管膜104及純 碳網格102，形成所述透射電鏡微栅1〇。 首先’提供一聚焦雷射光束，將該聚焦雷射光束照射至 所述至少一奈米碳管膜104及純碳網格102表面按預定尺 寸進行切割。本實施例中，雷射光束可通過傳統的氬離 子雷射器或二氧化碳雷射器產生，其功率為5〜30瓦（W)， 優選為18W。具體地，該雷射光束可通過一透鏡聚焦後從 正面直接照射在上述至少一奈米碳管膜1〇4及純碳網格 102表面’可以理解，該雷射光束可採用垂直照射或傾斜 照射聚焦於所述至少一奈米碳管膜104及純碳網格102表 面。所述至少一奈米碳管膜104及純碳網格102可吸收雷 射光束的能量從而與空氣中的氧發生反應並分解，從而 使具有預定尺寸的至少一奈米碳管膜104及純碳網格1〇2 099110666 表單編號A0101 第19頁/共32頁 0992018762-0 201135797 與其他部分斷開。本實施例中，切割後得到圓片狀至少 一奈米碳管膜104及純碳網格1〇2，其直徑約為3毫米。 [0062] 可以理解’上述切割步驟同樣可採用間隔照射所述片狀 奈米碳管結構中的方式來實現，如可固定所述至少一奈 米碳管膜104及純碳網格102，移動雷射光束；或固定雷 射光束，移動所述至少一奈米碳管膜104及純碳網格102 的方式來實現。另外，切割步驟中所述雷射光束聚焦照 射的時間可略長於在對片狀奈米碳管結構進行雷射打孔 時所述雷射光束聚焦照射的時間，以實現照射點處片狀 奈米碳管結構與其他部分片狀奈來碳管結構的完全分離 。本實施例並不限於上述雷射處理方法，先前技術中的 其他方法，如物理或化學刻蝕法，同樣可甩於切割所述 至少一奈米碳管膜104及純碳網袼102。 [0063] 可以理解，上述步驟可通過切割較大尺寸的至少一奈米 碳管臈104及純碳網格102 ’實現快疼批量生產透射電鏡 微拇1 0 〇 [0064] 本發明實施例提供的透射電鏡微栅及其製備方法具有以 下優點：其一，所述透射電鏡微柵由純碳網格及至少一 奈米碳管膜組成’無需金屬網格，且所述純碳網格及至 少一奈米碳管膜均較為純淨’可有效消除傳統微栅中的 金屬網格對被測樣品成份分析時的干擾，從而有利於提 高採用透射電鏡進行成份分析時的精確度。其二，本發 明實施例提供的透射電鏡微柵通過提供一純碳網格及至 少一奈米碳管膜並將該至少一奈米碳管膜鋪設在該純碳 網格表面來製備’無需蒸鍍過程，因此，製備方法較為 099110666 表單編號 A0101 第 20 頁/共 32 頁 0992018762-0 201135797 簡單。 [0065] 综上所述，本發明綠已符合發明專利之要件，遂依法提 出專利申請。惟’以上所述者僅為本發明之較佳實施例 ’自不能以此限制本案之申請專利範圍。舉凡習知本案 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】 [0066] 圖1為本發明實施例透射電鏡微柵的立體分解結構示意圖 〇 ... .... .. ...:: !L During the above stretching process, the plurality of carbon nanotube segments are gradually separated from the substrate in the tensile direction of the tensile force, and the selected plurality of carbon nanotube segments are respectively separated by the van der Waals force. The other carbon nanotube segments are continuously pulled out in an end-to-end manner to form a carbon nanotube film. The rotating carbon carbon film is a carbon nanotube film having a constant width formed by connecting a plurality of carbon nanotube segments arranged substantially in the stretching direction. The width of the carbon nanotube (four) is related to the size of the substrate on which the carbon nanotube array is grown. 'The length of the carbon nanotube film is not limited, and can be based on the actual 099110666 Form No. 1010101 Page / Total 32 Page 0992018762-0 [0049] [0049] [0050] [0050] Demand is made. The step of laminating and cross-setting a plurality of carbon nanotube drawn films may specifically include the following steps: First, providing a substrate. The substrate has a flat surface and its material is not limited. In this embodiment, the substrate can be a ceramic sheet. Next, the above-mentioned carbon nanotube film is laminated in this order and laid on the surface of the substrate. Since the carbon nanotubes are relatively pure and have a large specific surface area, the nanotubes obtained by directly pulling from the carbon nanotube array also have good viscosity. The carbon nanotube film can be directly laid on the surface of the substrate or on the surface of another carbon nanotube film. The so-called stacked vertical cross arrangement means that in the laminated carbon nanotube film, the carbon nanotubes in the plurality of carbon nanotube films have a crossing angle α and α is not equal to the twist. The adjacent two layers of nano-carbon film are tightly bonded by van der Waals force. In the embodiment, the forming of the plurality of meshes 1 〇6 may specifically include the following steps: a focused laser beam 'illuminates the focused laser beam point by line to the sheet-like carbon nanotube structure line by line in a predetermined pattern, at a position of the laser beam at the position of the <5-shaped carbon nanotube structure The carbon nanotubes are ablated to form a plurality of cells 1 . The plurality of cells 1〇6 are distributed in an array. The shape of the mesh is not limited to a circle, a square or an ellipse, etc. 099110666 Form No. Α0101 Page 16 of 32 0992018762-0 201135797 [0052] [0054] 005 [0054] Ο . In this embodiment, the shape of the mesh 106 is circular. The laser beam can be generated by a conventional argon ion laser or carbon dioxide laser. The power of the laser beam is 5 to 30 watts (W), preferably 18 watts. Specifically, the pulsed laser beam can be selected to form a plurality of cells 106 on the surface of the sheet-like carbon nanotube structure by progressive line-by-point scanning in a predetermined pattern. The plurality of cells 106 can be distributed in an array. Specifically, the following two methods can be used: Method 1: Fixing the sheet-shaped carbon nanotube structure, moving the laser beam, and irradiating the laser beam to the sheet-shaped carbon nanotube according to a predetermined pattern. Structural surface. Method 2: Fixing the laser beam, moving the sheet-shaped carbon nanotube structure, and irradiating the laser beam to the surface of the sheet-like carbon nanotube structure according to a predetermined pattern. It can be understood that the above moving and illuminating steps can be controlled by a computer program. The so-called "interval illumination" means that when the sheet-shaped carbon nanotube structure is laser-perforated, the laser beam is intermittently irradiated and irradiated to different positions of the sheet-shaped carbon nanotube structure, the difference The locations are spaced apart by a distance to ensure that a plurality of spaced apart meshes 106 are formed on the sheet of carbon nanotube structures. The cells 106 are distributed in an array. The mesh 106 can be a through hole, that is, the carbon nanotubes in the mesh 106 can remain. It can be understood that a portion of the carbon nanotubes may remain in the mesh 106, and the partial carbon nanotubes may also be used to support the sample to be tested. Step 2, providing at least one carbon nanotube film 104, and laying at least one carbon nanotube film 104 on the surface of the pure carbon mesh 102. 099110666 Form No. 101 0101 Page 17 / Total 32 Page 0992018762-0 [0055] [0056] The at least - nano tube film 1 〇 4 is preferably a carbon nanotube film, the carbon nanotube film The preparation method is the same as the preparation method of the carbon nanotube film formed by the sheet-shaped carbon nanotube structure. [0057] Since the carbon nanotubes are relatively pure and have a large specific surface area, the carbon nanotube film obtained by directly pulling from the carbon nanotube array has a good viscosity and the nano-pyrometer The film can be laid directly on the surface of the pure mesh 1 或 2 or another carbon nanotube film surface. When a plurality of carbon nanotube films are laid on the surface of the pure carbon grid 102, the plurality of carbon nanotube films may be laminated on the surface of the pure carbon grid 102 in a stack. The two adjacent layers of carbon nanotubes are tightly bonded by van der Waals force. In this embodiment, a four-layer carbon nanotube pull-film is sequentially laminated and disposed on the surface of the pure carbon grid 102. The angle between the carbon nanotubes in the adjacent two layers of carbon nanotube film is 90 degrees. The four-layer carbon nanotube film has a plurality of micropores 108. The pore size of the micropores 1〇8 may be from 1 nm to 丨μm. Further, the at least-carbon nanotube film 1〇4 and the pure carbon grid 102 may be treated with an organic solvent. The organic solvent is a volatile organic solvent at normal temperature, and one or a mixture of one of ethanol, methanol, acetone, urethane, and gas may be used. The organic solvent in this embodiment is ethanol. The organic solvent should have good wettability with the carbon nanotube. The step of treating with the organic solvent is specifically: dropping the organic solvent on the surface of the at least one carbon nanotube film 104 and the pure carbon mesh 102 through a test tube, or alternatively, the at least one carbon nanotube film 104 and the pure The carbon grid 1〇2 is immersed in a container containing an organic solvent to infiltrate. After the organic solvent treatment, the pure carbon grid 102 composed of carbon nanotubes is side by side and adjacent carbon nanotubes are gathered, and the pure carbon grid 102 has good mechanical strength. The at least one carbon nanotube film 099110666 Form No. A0101 Page 18 of 32 0992018762-0 201135797 Ο 104 After treatment with an organic solvent, some adjacent carbon nanotubes will aggregate to form a bundle of carbon nanotubes. The carbon nanotubes in the adjacent two-layer carbon nanotubes have a parent angle of '' and 0': 〇: S90. The carbon nanotube bundles in at least the 'τ' minocycline membrane 1 〇 4 after the organic solvent treatment are crossed to form a plurality of micropores 108. The size of the micropores 1 〇 8 is less than 1 〇 micrometer, preferably less than 1 micrometer. It can be understood that the more the number of at least one carbon nanotube film 104 laminated on the pure carbon grid 1〇2, the smaller the size of the micropores 1〇8. Therefore, the required size of the micropores 108 can be obtained by adjusting the number of the carbon nanotube membranes. Further, the at least one carbon nanotube film 104 can be combined with the pure carbon mesh 102 by an organic solvent treatment, so that the at least one carbon nanotube film 丨〇4 is more firmly fixed to the pure carbon mesh. On the grid 102. [0061] 〇 Step 3. Cutting the at least one carbon nanotube film 104 and the pure carbon mesh 102 by a predetermined size to form the TEM microgrid. First, a focused laser beam is provided, and the focused laser beam is irradiated onto the surface of the at least one carbon nanotube film 104 and the pure carbon grid 102 to be cut to a predetermined size. In this embodiment, the laser beam can be generated by a conventional argon ion laser or carbon dioxide laser having a power of 5 to 30 watts (W), preferably 18 watts. Specifically, the laser beam can be directly focused on the surface of the at least one carbon nanotube film 1〇4 and the pure carbon grid 102 from a front surface by focusing on a lens. It can be understood that the laser beam can be vertically illuminated or tilted. Irradiation is focused on the surface of the at least one carbon nanotube film 104 and the pure carbon grid 102. The at least one carbon nanotube film 104 and the pure carbon grid 102 can absorb the energy of the laser beam to react with and decompose the oxygen in the air, so that at least one carbon nanotube film 104 having a predetermined size and pure Carbon grid 1〇2 099110666 Form number A0101 Page 19 of 32 0992018762-0 201135797 Disconnected from other parts. In this embodiment, after cutting, at least one carbon nanotube film 104 and a pure carbon grid 1〇2 having a disk shape of about 3 mm are obtained. [0062] It can be understood that the above cutting step can also be implemented by intermittently irradiating the sheet-shaped carbon nanotube structure, such as fixing the at least one carbon nanotube film 104 and the pure carbon grid 102, and moving The laser beam or the fixed laser beam is moved by moving the at least one carbon nanotube film 104 and the pure carbon grid 102. In addition, the time during which the laser beam is focused and irradiated in the cutting step may be slightly longer than the time when the laser beam is focused and irradiated during laser drilling of the sheet-shaped carbon nanotube structure, so as to realize the sheet-shaped nai at the irradiation point. The carbon nanotube structure is completely separated from other parts of the sheet-like carbon nanotube structure. This embodiment is not limited to the above-described laser processing method, and other methods in the prior art, such as physical or chemical etching, can also be used to cut the at least one carbon nanotube film 104 and the pure carbon mesh 102. [0063] It can be understood that the above steps can achieve high-impact mass production of the transmission electron microscopy micro-bend 10 切割 by cutting a larger size of at least one carbon nanotube 臈 104 and a pure carbon grid 102 ′ [0064] The TEM micro-gate and the preparation method thereof have the following advantages: First, the TEM micro-gate is composed of a pure carbon grid and at least one carbon nanotube film, 'there is no metal grid, and the pure carbon grid and At least one carbon nanotube film is relatively pure', which can effectively eliminate the interference of the metal grid in the traditional micro-grid on the analysis of the components of the sample to be tested, thereby improving the accuracy of component analysis by TEM. Secondly, the TEM micro-gate provided by the embodiment of the present invention is prepared by providing a pure carbon grid and at least one carbon nanotube film and laying the at least one carbon nanotube film on the surface of the pure carbon mesh. The evaporation process, therefore, the preparation method is more 099110666 Form No. A0101 Page 20 / Total 32 Page 0992018762-0 201135797 Simple. [0065] In summary, the green of the invention has met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and the scope of the patent application of the present invention is not limited thereto. Equivalent modifications or variations made by those 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 [0066] FIG. 1 is a perspective exploded view of a TEM micro-gate according to an embodiment of the present invention. 〇.. . . .
[0067] 圖2為本發明貫施例透射電鏡微栅的立體結構示意圖。 [0068] 圖3為本發明實施例透射電鏡微柵的剖視結構示意圖。 [0069] 圖4為本發明實施例透射電鏡微柵中的奈米碳管序化膜的 掃描電鏡照片。 [0070] 圖5為本發明實施例透射電鏡微柵中的奈米碳管碾壓膜的 掃描電鏡照片。 [0071] 圖6為本發明實施例透射電鏡微柵中的奈米碳管拉膜的掃 描電鏡照片。 [0072] 圖7為本發明實施例透射電鏡微栅的製備方法的流程示意 圖。 【主要元件符號說明】 [0073] 透射電鏡微栅：1〇 [0074] 至少一奈米碳管膜：1〇4 0992018762-0 099110666 表單編號A0101 第21寅/共32頁 102 201135797 [0075] [0076] [0077] 純碳網格： 網孔：106 微孔：108 099110666 表單編號A0101 第22頁/共32頁 0992018762-02 is a schematic perspective view showing the structure of a transmission electron microscope micro-gate according to an embodiment of the present invention. 3 is a cross-sectional structural view of a TEM micro-gate according to an embodiment of the present invention. 4 is a scanning electron micrograph of a carbon nanotube sequential film in a transmission electron microstrip micro-gate according to an embodiment of the present invention. 5 is a scanning electron micrograph of a carbon nanotube rolled film in a transmission electron microstrip micro-gate according to an embodiment of the present invention. 6 is a scanning electron micrograph of a carbon nanotube film in a TEM microgrid according to an embodiment of the present invention. 7 is a schematic flow chart showing a method of fabricating a TEM microgate according to an embodiment of the present invention. [Main component symbol description] [0073] Transmission electron microstrip microgrid: 1〇[0074] At least one carbon nanotube film: 1〇4 0992018762-0 099110666 Form No. A0101 Page 21/32 List 102 201135797 [0075] [ 0076] [0077] Pure carbon grid: Mesh: 106 Micropores: 108 099110666 Form number A0101 Page 22 of 32 0992018762-0