201135798 六、發明說明： 【發明所屬之技術領威】 [0001] 本發明涉及一種透射電鏡微栅的製備方法，尤其涉及一 種基於奈米碳管的透射電鏡微柵的製傷方法。 【先前技術】 [0002] 在透射電子顯微鏡中，多孔碳支持膜（微柵）係用於承 載粉末樣品，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 奈米材料的電子顯微學表埤領$的應用日益廣泛。先前 〇 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，再蒸鍍一層 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，金存巧格因其經常 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。 [0003] 自九十年代初以來’以奈求碳管（請參見Helical mi- Q crotubules of graphitic carbon, Nature, Sum- io Iijima，vol 354，p56(i99丨））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 碳管應用於微柵的製作，有利於降低金屬網格對被測樣 品成份分析的干擾。 【發明内容】 [0004]有鑒於此’提供—種基於奈米碳管的透射電鏡微柵的製 備方法實為必要’所製備的透射電鏡微柵對被測樣品成 份分析的干擾較小。 0992018763-0 099110667 表單編號Α0101 第3頁/共27頁 201135798 [〇〇〇5] 一種透射電鏡微栅的製備方法，兮 咳方法包括以下步驟： 提供1狀奈Μ管結構；對所&狀奈織管結構進 打雷射打孔以形成複數個電子透射部；以及按預定尺寸 切割所述具有電子透射部的片狀夫 狀紊米碳管結構，形成所 述透射電鏡微柵。 _]相較於先前技術，本發明提供的Μ電鏡微柵通過對片 狀奈米碳管結構進行雷射打孔以Μ預定尺寸切割所述 片狀奈米碳管結構來製備，無需蒸錢過程，故，製備方 法較為簡單。所製備的透射電鏡微柵由圓片狀奈米碳管 結構組成，無需金屠網格，且奈米碳管結構較為純淨， 可有效消除傳统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】 [0007] 下面將結合附圖對本發明透射電鏡微柵及其製備方法作 進一步的詳細說明。 [0008] 請一併參閱圖1及圖2，本善明提供一種透射電鏡微柵10 。該透射電鏡微栅1 〇為一用於承載被測樣品的奈米碳管 結構。所述奈米碳管結構可為圓片狀，直徑約為3毫米^ 所述圓片狀奈米碳管結構為由複數個奈米碳管組成的自 支撐結構。所述圓片狀奈米碳管結構較為純淨，基本不 含有雜質。所述圓片狀奈米碳管結構包括一本體102及分 佈於本體102表面的複數個電子透射部104，該電子透射 部104的密度小於本體1〇2的密度° [0009] 所述本體102的表面具有複數個微孔108，每個微孔108 099110667 表單編號 Α0101 第 4 頁/共 27 貢 0992018763 0 201135798 Ο Ο 中具有複數個#米族管1G6。聲個微孔⑽對應、為^個電 子透射部1〇4。即，所述電子透射部104由設置於微孔 108中的夺米旅管106組成。所述電子透射部1〇4用於承 載被測樣射電軌察。所述電子透射部1〇4的密 度（電子透射部丨04中奈米碳管分佈的密度）可為所述本 體1〇2密度（本體1〇2中奈米碳管分佈的密度）的1/900 至1/10。優選地’所述電子透射部1〇4密度可為所述本體 102密度的1/500至1/10。所述電子透射部104巧·通過採 用雷射照射圓片狀奈米碳管結構的本體102形成。由於雷 射的作用，本體102被雷射照射位置的奈米碳管1〇6部分 被燒蝕，密度降低，形成微孔,1⑽，，進而形成電子透射部 104。依據選擇不同形狀的雷射光東或採用不同的雷射照 射方式，所述微孔1〇8的形狀不限；可選擇為圓形、方形 或橢圓形等。所述微孔1〇8的尺寸不限，可根據實際應用 需求調整。優選地’所述微孔1〇8為圓形孔所述微孔 108的直徑約為1〇微米〜2〇〇微米。所述複數個電子透射 部1υ4均勻分佈在所述本體1〇2表面，所述複數個電子透 射部104的排列方式不限。所述枒鄭的電子透射部1〇4之 間的距離可相4或不等。優選地，所述複數個電子透射 部104以陣列形式分佈在所述本體1〇2中，相鄰的電子透 射部10 4之間的距離相等。所述相鄰的電子透射部丨〇 4之 間的距離可大於1微米。 所述電子透射部104中的複數個奈米碳管1〇6用以支撐被 測樣品。所述電子透射部104中的奈米碳管1〇6為整個本 體102的一部分，與本體102為一體結構。具體地，所述 099110667 表單編號A0101 第5頁/共27頁 0992018763-0 [0010] 201135798 奈米碳管106可通過微孔108内壁的本體102支撐。具體 地，所述微孔108中的複數個奈米碳管106的兩端可插入 微孔108内壁的本體102中。所述複數個奈米碳管106可 平行設置或交叉設置。優選地，所述複數個奈米碳管106 空間交叉設置。交叉設置的複數個奈米碳管106之間進一 步形成複數個次微孔（圖未示）。該次微孔的孔徑在1奈 米〜1微米之間。所述微孔108中的奈米碳管106懸空設置 〇 [0011] 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。 [0012] 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。 [0013] 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 099110667 表單編號A0101 第6頁/共27頁 0992018763-0 201135798201135798 VI. Description of the Invention: [Technical Leadership of the Invention] [0001] The present invention relates to a method for preparing a transmission electron micro-gate, and more particularly to a method for injuring a transmission electron micro-gate based on a carbon nanotube. [Prior Art] [0002] In a transmission electron microscope, a porous carbon support membrane (microgrid) is an important tool for carrying a powder sample and performing a high-resolution image (HRTEM) observation of a transmission electron microscope. With the continuous development of nanomaterial research, micro-gates are increasingly used in the electron microscopy of nanomaterials. In the prior art, the microgrid applied to the transmission electron microscope is usually covered with a porous organic film on a metal mesh such as a copper mesh... or a nickel mesh, and then evaporated to a layer. Made 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, Jin Cunqiao often has more impurities, such as metal oxides, which interferes with the composition analysis of the sample to be tested. . [0003] Since the early 1990s, the nanomaterials represented by the carbon nanotubes (see Helical mi- Q crotubules of graphitic carbon, Nature, Sum io Iijima, vol 354, p56 (i99丨)) Its 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. SUMMARY OF THE INVENTION [0004] In view of the fact that this method of providing a TEM-based TEM micro-gate is really necessary, the prepared TEM micro-gate has less interference to the analysis of the sample component to be tested. 0992018763-0 099110667 Form No. Α0101 Page 3 of 27 201135798 [〇〇〇5] A method for preparing a transmission electron microstrip, the cough method includes the following steps: providing a 1-nap structure; The nye tube structure is laser-punched to form a plurality of electron-transmissive portions; and the sheet-shaped smear-shaped carbon nanotube structure having the electron-transmissive portion is cut to a predetermined size to form the TEM micro-gate. Compared with the prior art, the Μelectron micromirror provided by the present invention is prepared by laser drilling a sheet-shaped carbon nanotube structure to cut the sheet-shaped carbon nanotube structure in a predetermined size without steaming. Process, therefore, the preparation method is relatively simple. The prepared TEM micro-gate is composed of a disk-shaped carbon nanotube structure, which does not require a gold-scraping grid, and the nano-carbon tube structure is relatively pure, which can effectively eliminate the metal grid in the conventional micro-grid and analyze the composition of the sample to be tested. Time interference, which is beneficial to improve the accuracy of component analysis using TEM. [Embodiment] Hereinafter, a TEM microgate of the present invention and a preparation method thereof will be further described in detail with reference to the accompanying drawings. [0008] Referring to FIG. 1 and FIG. 2 together, Ben Shanming provides a TEM micro-gate 10 . The TEM microgrid 1 is a carbon nanotube structure for carrying a sample to be tested. The carbon nanotube structure may be in the form of a disk having a diameter of about 3 mm. The disk-shaped carbon nanotube structure is a self-supporting structure composed of a plurality of carbon nanotubes. The disk-shaped carbon nanotube has a relatively pure structure and contains substantially no impurities. The disk-shaped carbon nanotube structure includes a body 102 and a plurality of electron transmissive portions 104 distributed on the surface of the body 102. The density of the electron transmissive portion 104 is smaller than the density of the body 1〇2. [0009] The body 102 The surface has a plurality of micropores 108, each microporous 108 099110667 Form No. 101 0101 Page 4 / Total 27 Gong 0992018763 0 201135798 Ο Ο There are a plurality of #米族管1G6. The acoustic microholes (10) correspond to one electron transmitting portion 1〇4. That is, the electron-transmissive portion 104 is composed of a rice-carrying travel tube 106 disposed in the micro-hole 108. The electron transmissive portion 1〇4 is used to carry the radio track of the sample to be tested. The density of the electron-transmissive portion 1〇4 (the density of the distribution of the carbon nanotubes in the electron-transmissive portion 丨04) may be 1 of the bulk density of the bulk (the density of the distribution of the carbon nanotubes in the bulk 1〇2) /900 to 1/10. Preferably, the density of the electron-transmissive portion 1〇4 may be 1/500 to 1/10 of the density of the body 102. The electron-transmissive portion 104 is formed by irradiating a body 102 of a disk-shaped carbon nanotube structure with a laser. Due to the action of the laser, the body 102 is ablated by the carbon nanotube 1〇6 portion of the laser irradiation position, and the density is lowered to form micropores, 1 (10), thereby forming the electron-transmissive portion 104. The shape of the microholes 1〇8 is not limited according to the selection of laser light of different shapes or by different laser irradiation methods; and may be circular, square or elliptical. The size of the micro holes 1〇8 is not limited and can be adjusted according to actual application requirements. Preferably, the micropores 1 〇 8 are circular holes, and the micropores 108 have a diameter of about 1 μm to 2 μm. The plurality of electron-transmissive portions 1υ4 are evenly distributed on the surface of the body 1〇2, and the arrangement of the plurality of electron-transmissive portions 104 is not limited. The distance between the electron-transmission portions 1〇4 of the Zheng Zheng may be 4 or unequal. Preferably, the plurality of electron transmissive portions 104 are distributed in an array form in the body 1〇2, and the distance between adjacent electron-transmissive portions 104 is equal. The distance between the adjacent electron-transmissive portions 丨〇 4 may be greater than 1 μm. A plurality of carbon nanotubes 1〇6 in the electron transmissive portion 104 are used to support the sample to be tested. The carbon nanotubes 1〇6 in the electron-transmissive portion 104 are a part of the entire body 102 and are integrally formed with the body 102. Specifically, the 099110667 Form No. A0101 Page 5 of 27 0992018763-0 [0010] 201135798 The carbon nanotube 106 can be supported by the body 102 of the inner wall of the microhole 108. Specifically, both ends of the plurality of carbon nanotubes 106 in the micropores 108 can be inserted into the body 102 of the inner wall of the micropores 108. The plurality of carbon nanotubes 106 may be arranged in parallel or in a cross arrangement. Preferably, the plurality of carbon nanotubes 106 are spatially arranged in a cross. A plurality of sub-micropores (not shown) are further formed between the plurality of carbon nanotubes 106 disposed at the intersection. The pore size of the micropores is between 1 nm and 1 μm. The carbon nanotubes 106 in the micropores 108 are suspended. [0011] 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 can maintain its own sheet-like structure as long as it provides supporting force on both sides. The wafer-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. [0012] The carbon nanotube film may be a carbon nanotube film, a carbon nanotube film or a carbon nanotube film. [0013] 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 by Van der Waals force. 099110667 Form No. A0101 Page 6 of 27 0992018763-0 201135798
[0014] Ο 、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3。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200 844041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 —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。所述奈米碳營結構可僅包括一層奈米碳管絮化膜 ’通過調節其厚絲確保其具仙好的支禮性能。 所述奈米碳管碾_包純數崎來碳管無序排列、沿 個方向擇優取向排Μ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。該奈米碳管礙展 膜可以通過採用-平面壓頭沿垂真於上述奈米碳管陣列 生長的基底的方向掩壓上述奈米碳管陣列而獲得，此時 所述奈米碳《壓_的奈米碳管無序㈣，該奈米碳 s礙壓膜各向同!·生’所述奈求碳管碟壓膜也可以採用一 滾轴狀壓頭沿某1定方㈣壓上述奈米碳管陣列而獲 得，此時所述奈米唉管㈣膜中的奈米碳管在所述固定 方向擇優取向排列’所述奈米碳管礙壓膜還可以採用滾 軸狀壓頭料同方㈣壓上述奈米碳管陣⑽獲得，此 時所述奈米碳㈣壓”的奈米碳管沿不时向擇優取 向排列此時’所述奈米碳管減膜可包括概個部分， 每個部分中的奈錢管沿-個方向擇優取向排列，且相 099110667 表單編號A0101 第 頁/共27頁 0992018763-0 201135798 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4。所述奈米碳管碾 壓膜及其製備方法請參見於2009年1月1日公開的第 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。 [0015] 請參見圖5，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 管的整體延伸方向基本朝同一方向。而且，所述大多數 奈米碳管的整體延伸方向基本平行於奈米碳管拉膜的表 面。進一步地，所述奈米碳管拉膜中多數奈米碳管係通 過凡德瓦爾力首尾相連。具體地，所述奈米碳管拉膜中 基本朝同一方向延伸的大多數奈米碳管中每一奈米碳管 與在延伸方向上相鄰的奈米碳管通過凡德瓦爾力首尾相 連。當然，所述奈米碳管拉膜中存在少數隨機排列的奈 米碳管，這些奈米碳管不會對奈米碳管拉膜中大多數奈 米碳管的整體取向排列構成明顯影響。所述自支撐為奈 米碳管拉膜不需要大面積的載體支撐，而只要相對兩邊 提供支撐力即能整體上懸空而保持自身膜狀狀態，即將 該奈米碳管拉膜置於（或固定於）間隔一定距離設置的 兩個支撐體上時，位於兩個支撐體之間的奈米碳管拉膜 099110667 表單編號A0101 第8頁/共27頁 0992018763-0 201135798 能夠懸空保持自身膜狀狀態。所述自支撐主要通過奈米 碳管拉膜中存在連續的通過凡德瓦爾力首尾相連延伸排 列的奈求碳管而實現。 [0016]具體地，所述奈米碳管拉膜中基本朝同一方向延伸的多 數奈米碳管並非絕對的直線狀，可以適當的彎曲；戋者 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 0 接觸。具體地，每一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。該複數猶奈米碳管片段通 過凡德瓦爾力首尾相連。每一奈米碳管片,段包括複數個 基本相互平行的奈米碳管，該複數個基本相互平行的奈 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。所埤奈米碳管拉 膜為從一奈米碳管陣列中拉取獲得。根據奈米碳管陣列 〇 中奈米碳管的高度與密度的*同’所述奈米碳管拉膜的 厚度為0.5奈来〜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。所述奈米碳管拉膜的結構及其製備方法請參見於 2008年8月16日公開的第200833862號中華民國公開專 利申請。當所述奈来礙管膜的厚度為5奈米]〇〇微米時 *，所述奈米碳管結構可包括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。 099110667 表單編號Α0101 第9頁/共27頁 0992018763-0 201135798 [0017] 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。 [0018] 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 且小於等於90度。 [0019] 本實施例中，所述圓片狀奈米碳管結構包括100層奈米碳 管拉膜，且相鄰兩層奈米碳管膜中的奈米碳管之間具有 一交叉角度α，且該α等於90度。所述圓片狀奈米碳管 結構由一本體102及分佈於本體102表面的複數個電子透 射部104組成。所述本體102表面具有複數個圓形微孔 108。每個電子透射部104由對應於每個圓形微孔108中 的複數個奈米碳管106組成。該電子透射部104密度為所 述本體102密度的五十分之一（1/50)。所述圓形微孔 108的孔徑在30微米~ 150微米之間。所述微孔108中的複 數個奈米碳管106交叉設置形成複數個次微孔。該次微孔 099110667 表單編號Α0101 第10頁/共27頁 0992018763-0 201135798 [0020] Ο Ο [0021] [0022] [0023] 的孔徑為10G奈米。由於本實施例巾的透射電鏡微概⑽ 由奈米碳管結構組成，不含有金屬網格，且奈米碳管妗 構較為純淨，對被測樣品成份分析基本無干擾，因此， 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，從而有利於提高透射電鏡1〇進行成份分析時 的精確度。 本實施例透射電鏡微栅10在應用時，待觀察的材料樣品 承放在所述圓片狀奈米碳管結構表面。當所述材料樣品 的尺寸大於所述®片狀奈米碳管結構職孔1()8時所述 圓片狀奈来碳管結構中_孔丨〇 8可以支援該材料樣品。 可通過對應於微孔1〇8的電子透射部⑽觀測該材料樣品 。而當所述材料樣品的尺寸小於所述圓片狀奈米碳管結° 構的微孔1G8時，尤其當所述材料樣品為粒徑小於5奈米 的不米顆粒時’所述材料樣品可通過位於微孔⑽中的奈 米碳管106的吸附作用被穩定地吸附在奈米碳管⑽管壁 表面’此時’’料通過對應於微孔m的電子透射部1〇4 觀測該材料樣品Λ從而，本發明的透射電鏡微柵可實現 用於觀測粒徑小於5奈㈣奈米顆粒材料樣品，從而消除 傳統微柵巾的非晶销對純小於5奈㈣奈㈣粒的透 射電鏡鬲分辨像觀察的影響。 請參閱圖6，本發料-步提供料透㈣賴柵的製備 方法，其包括以下步驟： 步驟一，提供-片狀奈米碳管結構。 所述片狀奈米碳管結構由至少—奈来碳管膜組成 。所述 099110667 表單編號Α0101 第11頁/共27頁 0992018763-0 201135798 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通過 相互交叉地層疊設置（即層疊且交叉設置）多層奈米碳 管拉膜而形成，該奈米碳管拉膜為從一奈米碳管陣列中 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。 [0024] 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 ，在保護氣體環境下加熱到500~740°C，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 高度為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 粒等。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。 [0025] 本實施例中碳源氣可選用乙炔等化學性質較活潑的碳氫 099110667 表單編號A0101 第12頁/共27頁 0992018763-0 201135798 化合物，保護氣體可選用氮氣、氨氣或惰性氣體。 [0026] 採用一拉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 選定一定寬度的複數個奈米碳管片斷，本實施例優選為 採用具有一定寬度的膠帶接觸奈米碳管陣列以選定一定 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 ，以形成一奈米碳管膜。 Ο _ 在上述拉伸過程中，該複數個奈米碳管片斷在拉力作用 下沿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，從而形成一奈米碳管拉 膜。該奈米碳管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一定寬度的奈米碳管膜 。該奈米碳管拉膜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 Ο 需求制得。 [0028] 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： [0029] 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。 [0030] 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。所謂層疊且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 099110667 表單編號A0101 第13頁/共27頁 0992018763-0 201135798 一父又角度α且α不等於〇度。 酬ά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 性。所述奈米碳管拉膜可直接鋪設在基體表面或另一奈 米石反官拉祺表面。具體地，可將奈米碳管拉膜依次交叉 在斤述基體表面。相鄰兩層奈米碳管拉膜之間通過 凡德瓦爾力緊密結合。 [_步驟二、對所述片狀奈米碳管結構進行雷射打孔以形成 複數個電子透射部104。 _3]本實施例中，所述複數個電子透射部的形成方式具體 包括以下步驟： ^ 冑供—聚焦雷射光束。該雷射光東可通過傳統的 乳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15W。 [0035] : 將所述聚焦雷射光束按釋預定圖形逐行逐點聚焦 <、射至所述片狀奈求碳管結構表面，調節所述雷射光束 @力率使所述聚焦雷射光束照射位置處的片狀奈米碳管 構中。Ρτ?奈米峡管被燒μ，密度降低，形成微孔1〇8。 # \108中殘留有部分奈求碳管刚，從而形成按預定圖 ^佈的複數個相互間隔的電子透射部。所述複數個 電子透射部1〇4成陣列分佈。所述殘留的部分奈米碳管 106的數1以能夠較好地支揮樣品顆粒為佳。 099110667 '也1選擇脈衝雷射光束按照預定圖形採用逐行逐 •’掃也的方式實現照射片狀奈米碳管結構的表面形成複 單編親_1 第U頁/共27頁 〇992〇18763-0 [0036] 201135798 [0037] [0038] [0039]Ο [0040] Ο [0041] 數個微孔108。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， 使雷射光束按照預定圖形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， 使雷射光束按照預定圖形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 設置的微孔108。所述複數個微孔108成陣列分佈。 當雷射光束間隔照射至所述片狀奈米碳管結構表面時， 由於片狀奈米碳管結構中的奈米碳管對雷射具有較好的 吸收特性，雷射照射處的片狀奈米碳管結構中的複數個 奈米碳管聚集形成的奈米碳管束將會因吸收較多的熱量 而首先被燒毀。其次，根據雷射的不同功率，片狀奈米 碳管結構中不同直徑的奈米碳管束，甚至單個奈米碳管 也將被燒毀。本發明通過調整雷射光束的功率為5~30瓦 (W)來實現所形成的微孔108中殘留部分奈米碳管106。 該微孔108中的奈米碳管106可用於支撐被測樣品，並形 成所述電子透射部104。 步驟三、按預定尺寸切割所述具有電子透射部104的片狀 099110667 表單編號Α0101 第15頁/共27頁 0992018763-0 201135798 奈米碳管結構，形成所述透射電鏡微栅1 〇。 [0042] 首先，提供一雷射光束。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。 [0043] 其次，將該雷射光束聚焦照射至具有複數個電子透射部 104的片狀奈米碳管結構表面進行切割，形成預定形狀與 尺寸的透射電鏡微柵10。該雷射光束可通過一透鏡聚焦 後從正面直接照射在上述片狀奈米碳管結構表面，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 述片狀奈米碳管結構表面。所述片狀奈米碳管結構吸收 雷射光束能量從而與空氣中的氧發生反應並分解，從而 使具有預定形狀與尺寸的片狀奈米碳管結構與其他部分 片狀奈米碳管結構斷開。本實施例中，所述切割後得到 圓片狀奈米碳管結構，其直徑約為3毫米。 [0044] 可以理解，上述切割步驟同樣可採用步驟三中固定所述 片狀奈米碳管結構，移動雷射光束；或固定雷射光束， 移動所述片狀奈米碳管結構的方式來實現。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 米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 ，同樣可用於切割片狀奈米碳管結構。 [0045] 可以理解，上述步驟可通過切割較大尺寸的片狀奈米碳 099110667 表單編號Α0101 第16頁/共27頁 0992018763-0 201135798 管結構，實現快速批量生產透射電鏡微柵1〇。具艘地’ 可按預定圖形將所述雷射光束聚焦照射至具有電子透射 部的片狀奈米碳管結構，按預定尺寸對片狀奈米碳管結 構進行切割，形成複數個圓片狀奈米碳管結構，#個圓 片狀奈米碳管結構具有複數個電子透射部1 〇4。 [0046] Ο ο 所述透射電鏡微柵10可進一步經有機溶劑處理。該有機 溶劑為常溫下易揮發的有機溶劑，可選用乙酵、甲醉、 丙酮、二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酵。該有機溶劑應與該奈米破管 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透射電鏡微柵1 〇表面浸潤 整個片狀奈米碳管結構，或者，將上述透射電鏡微柵10 浸入盛有有機溶劑的容器中浸潤。有機溶劑處理後的透 射電鏡微柵10的本體中並排且相鄰的奈米碳管會聚攏， 具有較好的機械強度。此外，所述微孔108中的複數個奈 求碳管106在有機溶劑處理後，部分相鄰的奈米碳管會聚 集成奈米碳管束。複數個奈米碳管束之間可進一步形成 複數個次微孔。該次微孔的孔徑可為1奈米〜1微米。可以 理解’所述有機溶劑的步驟也可在切割步驟之前進行， 即可先對所述具有電子透射部104的片狀奈米碳管結構進 行有機溶劑處理，然後再切割成圓片狀奈米碳管結構。 [0047] 本發明實施例提供的透射電鏡微柵及其製備方法具有以 下優點：其一，所述透射電鏡微栅由圓片狀奈米碳管結 構組成，無需金屬網格，且圓片狀奈米碳管結構較為純 淨’可有效消除傳統微柵中的金屬網格對被測樣品成份 099110667 表單編號Α0101 第17真/共27頁 0992018763-0 201135798 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 微栅通過對片狀奈米碳管結構進行雷射打孔以及按預定 尺寸切割所述片狀奈米碳管結構來製備，無需蒸鐘過程 ，因此，製備方法較為簡單。 [0048] 綜上所述，本發明確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清專利範圍。舉凡習知本幸 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】 [0049] 圖1為本發明實施例透射電鏡微栅的立體結構示意圖。 [0050] 圖2為本發明實施例透射電鏡微栅的剖視結構示意圖。 [0051] 圖3為本發明實施例透射電鏡微柵中的奈米碳管絮化膜的 掃描電鏡照片。 ： ί ...[0014] Ο, entangled 'forms a network-like structure to form a self-supporting carbon nanotube flocculating membrane'. See FIG. 3 for a scanning electron micrograph. 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 can be found in the 200th published on November 16, 2008. No. 844041, the Republic of China open patent application. 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 nanocarbon camp structure may include only one layer of carbon nanotube flocculation film 'by adjusting its thick wire to ensure its good brittle performance. The carbon nanotubes of the carbon nanotubes are randomly arranged in a random order, and the preferred orientations along the direction are arranged in a plurality of directions, and the adjacent carbon nanotubes are combined by van der Waals force. The carbon nanotube barrier film can be obtained by masking the carbon nanotube array in a direction in which the substrate is grown in the direction of the substrate grown by the carbon nanotube array, and the nano carbon "pressure" _ The carbon nanotubes are disordered (4), the nano-carbon s-pressure film is the same! · The raw 'the carbon tube disc pressure film can also use a roller-shaped pressure head along a certain square (four) pressure Obtained by the above-mentioned carbon nanotube array, in which the carbon nanotubes in the nanotube (four) film are preferentially aligned in the fixed direction. The carbon nanotube film can also adopt a roller-shaped pressure. The headstock is the same as the square (4) obtained by pressing the above-mentioned nano carbon tube array (10). At this time, the carbon nanotubes of the nano carbon (four) pressure are arranged along the preferred orientation from time to time. In part, the nemesis tubes in each section are arranged in a preferred orientation along the direction of the direction, and the phase 099110667 Form No. A0101 Page 27/Total 27 Page 0992018763-0 201135798 The arrangement of the carbon nanotubes in the two adjacent sections may be different. The scanning electron micrograph of the carbon nanotube rolled film is shown in Figure 4. The carbon nanotube film and its For the preparation method, please refer to the Chinese Patent Application No. 200900348 published on January 1, 2009. To save space, only the above is cited, but all the technical disclosures in the application should also be regarded as the disclosure of the technical application of the present application. In part, the carbon nanotube rolled film has a thickness of 1 micrometer to 1 millimeter. The carbon nanotube structure may include only one layer of carbon nanotube rolled film, and the thickness thereof is adjusted to achieve better. [0015] Referring to Fig. 5, the carbon nanotube film is a self-supporting structure composed of a plurality of carbon nanotubes, and the plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. Orientation means that the overall extension direction of most of the carbon nanotubes in the carbon nanotube film is substantially in the same direction. Moreover, the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the film of the carbon nanotube film. Further, most of the carbon nanotubes in the carbon nanotube film are connected end to end by van der Waals force. Specifically, most of the nano carbon nanotubes are stretched in the same direction. Each in the carbon tube The carbon nanotubes and the carbon nanotubes adjacent in the extending direction are connected end to end by Van der Waals force. Of course, there are a few randomly arranged carbon nanotubes in the carbon nanotube film, and these carbon nanotubes are present. It does not significantly affect the overall orientation of most of the carbon nanotubes in the carbon nanotube film. The self-supporting carbon nanotube film does not require a large area of carrier support, but only provides support on opposite sides. That is, the whole can be suspended to maintain its own membranous state, that is, when the carbon nanotube film is placed (or fixed) on two supports arranged at a certain distance, the nanocarbon between the two supports Tube film 099110667 Form No. A0101 Page 8 of 27 0992018763-0 201135798 Can be suspended to maintain its own membranous state. The self-supporting is mainly achieved by the presence of continuous carbon nanotubes extending through the end of the van der Waals force through the carbon nanotube film. [0016] Specifically, most of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film are not absolutely linear, and may be appropriately bent; the latter are not completely aligned in the extending direction, and may be appropriately Deviate from the direction of extension. Therefore, there may be a partial 0 contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes which extend substantially in the same direction of the carbon nanotube film. Specifically, each carbon nanotube film comprises a plurality of carbon nanotube segments arranged in a continuous and preferred orientation. The plurality of duplicate carbon nanotube segments are connected end to end by Van der Valli. Each nano carbon tube segment includes a plurality of substantially parallel carbon nanotubes, and the plurality of substantially parallel carbon nanotubes are tightly coupled by van der Waals force. The carbon nanotube segments have any 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 obtained by pulling from a carbon nanotube array. 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 and pull of the carbon nanotube film are drawn. The size of the carbon nanotube array in which the carbon nanotube film is taken is not limited in length. The structure of the carbon nanotube film and the preparation method thereof can be referred to the application of the Republic of China open patent No. 200833862, published on August 16, 2008. When the thickness of the Nai tube film is 5 nm] 〇〇 micrometers, the carbon nanotube structure may include a carbon nanotube film laminated in the above. Preferably, the carbon nanotube structure may include a carbon nanotube film laminated over 100 layers. 099110667 Form No. 1010101 Page 9 of 27 0992018763-0 201135798 [0017] When the disk-shaped carbon nanotube structure comprises a plurality of carbon nanotube membranes and the carbon nanotubes in each carbon nanotube membrane When aligned in the same direction, the arrangement direction of the carbon nanotubes in the adjacent two layers of carbon nanotube film may be the same or different. Specifically, the carbon nanotubes in the adjacent carbon nanotube film have an intersection angle α between the α and the α is greater than or equal to 0 degrees and less than or equal to 90 degrees. When the carbon nanotubes in the plurality of carbon nanotube membranes in the disk-shaped carbon nanotube structure have an intersection angle α and α is not equal to 0 degrees, that is, when a plurality of carbon nanotube 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. [0018] It can be understood that the plurality of carbon nanotube membrane cross-settings does not require any two adjacent carbon nanotube membranes to be cross-overly disposed, that is, the majority of the adjacent two layers of carbon nanotube membranes are allowed to exist. Where the arrangement of the carbon tubes is the same, but it is necessary to ensure that the intersection angle between the arrangement directions of the majority of the carbon nanotubes in at least two layers of the carbon nanotube membrane is greater than 0 degrees and less than Equal to 90 degrees. [0019] In the embodiment, the disk-shaped carbon nanotube structure comprises a 100-layer carbon nanotube film, and the carbon nanotubes in the adjacent two layers of carbon nanotube film have an intersection angle therebetween. α, and the α is equal to 90 degrees. The disk-shaped carbon nanotube structure is composed of a body 102 and a plurality of electron-transmissive portions 104 distributed on the surface of the body 102. The surface of the body 102 has a plurality of circular micropores 108. Each of the electron transmissive portions 104 is composed of a plurality of carbon nanotubes 106 corresponding to each of the circular micropores 108. The electron transmissive portion 104 has a density of one-fiftieth (1/50) the density of the body 102. The circular micropores 108 have a pore size between 30 microns and 150 microns. A plurality of carbon nanotubes 106 in the micropores 108 are arranged to form a plurality of secondary micropores. The micropore 099110667 Form No. Α0101 Page 10/Total 27 Page 0992018763-0 201135798 [0020] [0022] [0023] The aperture is 10G nanometer. Since the transmission electron microscopy (10) of the towel of the present embodiment is composed of a carbon nanotube structure, does not contain a metal mesh, and the carbon nanotube structure is relatively pure, and the composition of the sample to be tested is basically free from interference, thereby effectively eliminating the conventional The metal grid in the micro-grid interferes with the analysis of the components of the sample to be tested, which is beneficial to improve the accuracy of the composition analysis of the transmission electron microscope. In the embodiment, the TEM microgrid 10 is applied, and the material sample to be observed is placed on the surface of the disk-shaped carbon nanotube structure. The material sample is supported in the wafer-shaped carbon nanotube structure when the size of the material sample is larger than the sheet-like carbon nanotube structure hole 1 () 8 . The material sample can be observed through the electron transmissive portion (10) corresponding to the microholes 1〇8. And when the size of the material sample is smaller than the microporous 1G8 of the wafer-shaped carbon nanotube structure, especially when the material sample is a non-rice particle having a particle diameter of less than 5 nm It can be stably adsorbed on the surface of the wall of the carbon nanotube (10) by the adsorption of the carbon nanotubes 106 located in the micropores (10). At this time, the material is observed through the electron-transmissive portion 1〇4 corresponding to the micropores m. The sample of the material Λ thus, the TEM microgrid of the present invention can be used to observe a sample of a particle material having a particle diameter of less than 5 nanometers (four), thereby eliminating the transmission of the amorphous pin of the conventional micro-gear to a purity of less than 5 nanometer (four) nai (four) particles. Electron microscopy 鬲 resolves the effects of image observation. Referring to Figure 6, the present invention provides a method for preparing a feedthrough (four) barrier, which comprises the following steps: Step one, providing a sheet-like carbon nanotube structure. The sheet-like carbon nanotube structure is composed of at least a carbon nanotube film. The 099110667 Form No. Α0101 Page 11 of 27 0992018763-0 201135798 The carbon nanotube film can be a carbon nanotube film, a carbon nanotube film or a carbon nanotube film. In this embodiment, the sheet-like carbon nanotube structure is formed by laminating (ie, laminating and intersecting) a plurality of layers of carbon nanotube film which are formed from a nano carbon. The tube array is pulled and obtained. 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. [0024] 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 In the protective gas atmosphere, the temperature is heated to 500-740 ° C, and then the carbon source gas is introduced for about 5 to 30 minutes to grow to obtain a super-sequential carbon nanotube array having a height of 200 to 400 μm. The super-sequential carbon nanotube array is a plurality of pure carbon nanotube arrays formed of carbon nanotubes that are parallel to each other and grown perpendicular to the substrate. The super-sequential carbon nanotube array is substantially free of impurities such as amorphous carbon or residual catalyst metal particles by the above controlled growth conditions. The carbon nanotubes in the array of carbon nanotubes are in close contact with each other to form an array by van der Waals forces. [0025] In the present embodiment, the carbon source gas may be selected from acetylene and other chemically active hydrocarbons. 099110667 Form No. A0101 Page 12 of 27 0992018763-0 201135798 Compound, the protective gas may be selected from nitrogen, ammonia or inert gas. The step of extracting the carbon nanotube film from the carbon nanotube array by using a stretching tool specifically includes the following steps: (a) selecting a plurality of nano carbons of a certain width from the carbon nanotube array. The tube segment, in this embodiment, preferably adopts a tape having a certain width to contact the carbon nanotube array to select a plurality of carbon nanotube segments of a certain width; (b) along a growth direction substantially perpendicular to the growth direction of the carbon nanotube array The plurality of carbon nanotube segments are stretched to form a carbon nanotube film. Ο _ During the above stretching process, the plurality of carbon nanotube segments are gradually separated from the substrate in the stretching direction under the tensile force, and the selected plurality of carbon nanotube segments are respectively caused by the van der Waals force The other carbon nanotube segments are continuously pulled out end to end to form a carbon nanotube film. The carbon nanotube film is a carbon nanotube film having a certain width formed by connecting a plurality of carbon nanotube segments arranged substantially in the stretching direction. The width of the carbon nanotube film 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 obtained according to actual enthalpy requirements. [0028] The step of laminating and cross-setting a plurality of carbon nanotube film may specifically include the following steps: [0029] First, a substrate is provided. The substrate has a flat surface and its material is not limited. In this embodiment, the substrate can be a ceramic sheet. [0030] Next, the above-mentioned carbon nanotube film is laminated in this order and laid on the surface of the substrate. The so-called stacking and cross-setting means that in the laminated carbon nanotube film, the carbon nanotubes in the plurality of carbon nanotube films have 099110667 between them. Form No. A0101 Page 13 / Total 27 Page 0992018763-0 201135798 A parent has an angle α and α is not equal to the degree. The carbon nanotubes obtained from the carbon nanotube array are relatively pure and have a large specific surface area. Therefore, the carbon nanotube film obtained by directly drawing from the carbon nanotube array has good viscosity. The carbon nanotube film can be directly laid on the surface of the substrate or on the surface of another nano-rock. Specifically, the carbon nanotube film can be sequentially crossed on the surface of the substrate. Adjacent two layers of carbon nanotubes are tightly bonded by van der Waals force. [_Step 2] Laser-perforating the sheet-like carbon nanotube structure to form a plurality of electron-transmissive portions 104. In the embodiment, the forming manner of the plurality of electron transmissive portions specifically includes the following steps: ^ 胄 supply-focusing the laser beam. The laser light can be generated by a conventional emulsion ion laser or a carbon dioxide laser. The laser beam has a power of 5 to 30 watts (W), preferably 15 watts. [0035]: focusing the focused laser beam in a row-by-point manner on a predetermined pattern, and projecting onto the surface of the sheet-like carbon tube structure, adjusting the laser beam@force rate to cause the focused beam The sheet-shaped carbon nanotube structure at the position where the beam is irradiated. Ρτ? The nano-gorge tube is burnt μ, and the density is lowered to form micropores 1〇8. There is a portion of the carbon nanotubes remaining in #\108, thereby forming a plurality of mutually spaced electron-transporting portions according to a predetermined pattern. The plurality of electron transmissive portions 1〇4 are distributed in an array. The number 1 of the remaining partial carbon nanotubes 106 is preferably such that the sample particles can be favorably supported. 099110667 'Also 1 selects the pulsed laser beam to realize the surface formation of the sheet-like carbon nanotube structure according to the predetermined pattern by means of the line-by-line sweeping method. The U-page/Total 27 pages 〇992〇 18763-0 [0036] 201135798 [0037] [0040] [0040] [0041] A plurality of microholes 108. 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 interval. 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-shaped carbon nanotube structure at a predetermined pattern interval. It will 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 to ensure that a plurality of spaced apart apertures 108 are formed in the sheet of carbon nanotube structure. The plurality of microwells 108 are distributed in an array. When the laser beam is irradiated to the surface of the sheet-like carbon nanotube structure at intervals, since the carbon nanotubes in the sheet-shaped carbon nanotube structure have good absorption characteristics for the laser, the sheet of the laser irradiation is The carbon nanotube bundle formed by the aggregation of a plurality of carbon nanotubes in the carbon nanotube structure will be first burned by absorbing more heat. Secondly, according to the different power of the laser, the carbon nanotube bundles of different diameters in the sheet-like carbon nanotube structure, even a single carbon nanotube, will be burned. The present invention realizes the remaining portion of the carbon nanotubes 106 in the formed micropores 108 by adjusting the power of the laser beam to 5 to 30 watts (W). The carbon nanotubes 106 in the micropores 108 can be used to support the sample to be tested and form the electron transmissive portion 104. Step 3: Cutting the sheet having the electron transmissive portion 104 according to a predetermined size. 099110667 Form No. 1010101 Page 15/27 Page 0992018763-0 201135798 The carbon nanotube structure forms the TEM microgrid 1 〇. [0042] First, a laser beam is provided. 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. [0043] Next, the laser beam is focused and irradiated onto the surface of the sheet-shaped carbon nanotube structure having a plurality of electron-transmissive portions 104 for cutting to form a transmission electron micro-mirror 10 of a predetermined shape and size. The laser beam can be directly focused on the surface of the sheet-shaped carbon nanotube structure from the front surface after being focused by a lens. It can be understood that the laser beam can be focused on the sheet-shaped carbon nanotube structure by vertical illumination or oblique illumination. surface. The sheet-like carbon nanotube structure absorbs the energy of the laser beam to react with and decompose the oxygen in the air, thereby forming the sheet-shaped carbon nanotube structure having a predetermined shape and size and other partial sheet-like carbon nanotube structures. disconnect. In this embodiment, after the cutting, a disk-shaped carbon nanotube structure having a diameter of about 3 mm is obtained. [0044] It can be understood that the above cutting step can also adopt the method of fixing the sheet-shaped carbon nanotube structure in step 3, moving the laser beam, or fixing the laser beam, and moving the sheet-shaped carbon nanotube structure. achieve. 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 to realize the sheet-shaped carbon carbon at the irradiation point. The tube structure is completely separated from other parts of the sheet-like carbon nanotube structure. This embodiment is not limited to the above laser processing method, and other methods in the prior art, such as physical or chemical etching, can also be used to cut the sheet-like carbon nanotube structure. [0045] It can be understood that the above steps can be achieved by cutting a large-sized sheet-shaped nanocarbon 099110667 Form No. Α0101 Page 16/27 Page 0992018763-0 201135798 tube structure to realize rapid mass production of TEM micro-gates. The ship's beam can be focused and irradiated to a sheet-like carbon nanotube structure having an electron-transmissive portion in a predetermined pattern, and the sheet-shaped carbon nanotube structure is cut to a predetermined size to form a plurality of discs. The carbon nanotube structure, the #1 piece-shaped carbon nanotube structure has a plurality of electron-transmissive portions 1 〇4. [0046] The TEM microgrid 10 may be further treated with an organic solvent. The organic solvent is a volatile organic solvent at normal temperature, and may be a mixture of one or a combination of ethyl lactate, intoxication, acetone, di-ethane and gas, and the organic solvent in the present embodiment is ethyl lactate. The organic solvent should have good wettability with the nanotube. The step of treating with an organic solvent is specifically: dipping the organic solvent onto the surface of the TEM micro-gate 1 through a test tube to infiltrate the entire sheet-shaped carbon nanotube structure, or immersing the TEM micro-gate 10 in an organic solvent. Infiltrated in the container. The organic carbon-treated micro-mirrors 10 are arranged side by side and the adjacent carbon nanotubes are gathered together to have good mechanical strength. In addition, after the plurality of carbon nanotubes 106 in the micropores 108 are treated with an organic solvent, a portion of the adjacent carbon nanotubes are aggregated into a bundle of carbon nanotubes. A plurality of secondary micropores may be further formed between the plurality of carbon nanotube bundles. The pore size of the micropores may be from 1 nm to 1 μm. It can be understood that the step of the organic solvent can also be carried out before the cutting step, that is, the sheet-shaped carbon nanotube structure having the electron-transmissive portion 104 is first subjected to an organic solvent treatment, and then cut into wafer-shaped nanoparticles. Carbon tube structure. The TEM micro-gate provided by the embodiment of the invention and the preparation method thereof have the following advantages: First, the TEM micro-gate is composed of a disk-shaped carbon nanotube structure, does not need a metal mesh, and has a disk shape The carbon nanotube structure is relatively pure' can effectively eliminate the metal grid in the traditional micro-grid on the sample component to be tested 099110667 Form No. Α0101 17th true / Total 27 pages 0992018763-0 201135798 Analysis of interference, which is conducive to improve the use of transmission The accuracy of the composition analysis by electron microscopy. Secondly, the TEM micro-gate provided by the embodiment of the present invention is prepared by performing laser drilling on the sheet-shaped carbon nanotube structure and cutting the sheet-shaped carbon nanotube structure by a predetermined size without a steaming process. The preparation method is relatively simple. [0048] In summary, the present invention has indeed 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. 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 [0049] FIG. 1 is a perspective view showing a three-dimensional structure of a transmission electron microscope micro-gate according to an embodiment of the present invention. 2 is a cross-sectional structural view of a TEM micro-gate according to an embodiment of the present invention. 3 is a scanning electron micrograph of a carbon nanotube flocculation film in a transmission electron microstrip micro-gate according to an embodiment of the present invention. : ί ...
[0052] 圖4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。 [0053] 圖5為本發明實施例透射電鏡微栅中的奈米碳管拉膜的掃 描電鏡照片。 [0054] 圖6為本發明實施例透射電鏡微栅的製锴方法的流程示意 圖。 【主要元件符號說明】 [0055] 透射電鏡微柵：10 099110667 表單編號Α0101 第18 "共27頁 0992018763-0 201135798 [0056] 本體：102 ：104 106 [0057] 電子透射部 [0058] 奈米碳管： [0059] 微孔：1084 is a scanning electron micrograph of a carbon nanotube rolled film in a TEM microgrid according to an embodiment of the present invention. 5 is a scanning electron micrograph of a carbon nanotube film in a transmission electron microscope micro-gate according to an embodiment of the present invention. 6 is a schematic flow chart of a method for manufacturing a TEM micro-gate according to an embodiment of the present invention. [Major component symbol description] [0055] Transmission electron microstrip: 10 099110667 Form number Α 0101 18 " Total 27 pages 0992018763-0 201135798 [0056] Body: 102: 104 106 [0057] Electron transmission section [0058] Nano Carbon tube: [0059] Microporous: 108
099110667 表單編號A0101 第19頁/共27頁 0992018763-0099110667 Form No. A0101 Page 19 of 27 0992018763-0