201103862 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栅及其製備方法。 【先前技術] [0002] 在透射電子顯微鏡中，非晶碳支持膜（微栅）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 奈米材料的電子顯微學表徵領域的應用日益廣泛。先前 ❹ 技術中，該應用於透射電子顯微鏡的微栅通常係在銅網 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，在實際應用中，尤其在觀察尺 寸爲奈米級的顆粒的透射電鏡高分辨像時，微栅中的非 • 晶碳膜較厚，襯度噪聲較大，對奈米顆粒的透射電鏡成 • 像分辨率的提高影響很大。 【發明内容】 [〇〇〇3]有鑒於此，提供一種透射電鏡微栅及其製備方法，其中 〇 該透射電鏡微栅對於奈米級顆粒，更容易獲得效果更好 地透射電鏡高分辨像實為必要。201103862 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a transmission electron microstrip microgrid and a method of fabricating the same. [Prior Art] [0002] In a transmission electron microscope, an amorphous carbon support film (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, microgrids are increasingly used in the field of electron microscopy characterization of 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 an amorphous carbon film. However, in practical applications, especially when observing the high-resolution image of the TEM of the nanometer-sized particles, the non-crystalline carbon film in the micro-gate is thick, the contrast noise is large, and the transmission electron microscope for the nano-particles The effect of the resolution is greatly affected. SUMMARY OF THE INVENTION [3] In view of the above, there is provided a TEM micro-grid and a preparation method thereof, wherein the TEM micro-gate is more likely to obtain a better TEM image with respect to nano-sized particles. It is really necessary.
[0005] 098126005 一種透射電鏡微栅，其包括一網格以及一石墨烯片_奈米 兔管膜複合結構覆蓋該網格，並通過該網格部分懸空設 置，該石墨烯片-奈米碳管膜複合結構包括至少一奈米碳 管膜結構及多個石墨稀片，該奈米碳管膜結構包括多個 微孔，其中，至少一微孔被一石墨烯片覆蓋。 一種透射電鏡微栅’其包括一網格，以及一石墨烯片一奈 米碳管膜複合結構覆蓋該網格，並通過該網格部分懸空 0982044562-0 表單編號A0101 第3頁/共33頁 201103862 設置’該石墨稀片-奈米碳管膜複合結構包括至少 =膜結構及多個石_，該奈_膜結構包括不多、 個奈米碳管線父叉設置以及由該多個交又設 管線形成的多個微孔，其中，至少_ 覆蓋。 置的奈米碳 微孔被一石墨烯片 [0006] [0007] Γ射㈣錢的製備方法，其包括以下步驟：提伊 2支撑的奈米碳管騎構，以及_石輯' 该奈米碳管膜結構包括多個微孔；將該石墨烯片分散液 :潤t奈米碳官膜結構表面;乾燥該被石烯片浸潤的 SC管=構二而使該，片與_碳管膜結 構複合奈米碳管膜複合結構；以及 所述石墨烯片-奈米碳管膜複合結構覆蓋一網格。 相較於先前技術’所述的透射電鏡微栅及其 通過從奈米碳管_拉取磐奈米碳管麟構並龄 奈米碳管麟構料―種具峰孔的紐㈣，通· 石墨料覆蓋在該支撑骨㈣微孔上，實現石墨稀片: 懸空設置。由於石墨烯片具有_的厚度，在透射電類 觀察中産生的襯度聲聲較小，從而可獲得 透射電鏡照片。 千衩阿㈤[0005] 098126005 A TEM microgrid comprising a grid and a graphene sheet-nano rabbit tubular composite structure covering the grid, and the grid portion is suspended by the grid portion, the graphene sheet-nanocarbon The tubular composite structure comprises at least one carbon nanotube membrane structure and a plurality of graphite thin films, the nanocarbon tubular membrane structure comprising a plurality of micropores, wherein at least one microporous is covered by a graphene sheet. A TEM microgrid comprising a grid and a graphene sheet-carbon nanotube film composite structure covering the grid and suspended by the grid portion 098204456-2-0 Form No. A0101 Page 3 of 33 201103862 Setting 'the graphite thin film-nano carbon tube film composite structure includes at least = membrane structure and a plurality of stones _, the nano membrane structure includes not many, a carbon carbon pipeline parent fork setting and by the plurality of intersections A plurality of micropores formed by the pipeline, wherein at least _ are covered. The nano carbon micropores are prepared by a graphene sheet [0006] [0007] Γ (4) money, which comprises the following steps: the Tiey 2 supported carbon nanotube riding, and the _石辑' The carbon nanotube film structure comprises a plurality of micropores; the graphene sheet dispersion liquid: moisturizing the surface of the carbon nano-membrane structure; drying the stone tube infiltrated by the alkene sheet = the second layer, the sheet and the carbon a tubular film structure composite nanocarbon tube film composite structure; and the graphene sheet-nano carbon tube film composite structure covers a grid. Compared with the TEM microgrid described in the prior art, and through the extraction of the nano-carbon nanotubes from the carbon nanotubes, the nano-carbon nanotubes, the peaks of the peaks, · Graphite material is covered on the support bone (4) micropores to achieve graphite thin film: suspended setting. Since the graphene sheet has a thickness of _, the contrast sound generated in the observation of the transmission type is small, so that a transmission electron microscope photograph can be obtained. Millennium (5)
[0008] 【實施方式】 下面將結合關及_實_對本發明提供的透 [0009] 請參閱圖1，本發日β 赞明第一實施例透射電鏡微栅的製備方 主要包括以下幾個步驟： 法 098126005 表單編號Α0101 第4頁/共33頁 〇982〇44562~〇 201103862 [0010] [0011] [0012] [0013]Ο ❹ [0014] 步驟一，提供一奈米碳管膜結構，以及一石墨烯片分散 液。 該奈米碳管膜結構包括多層交叉層叠的奈米碳管膜。該 奈米碳管膜爲從一奈米碳管陣列中直接拉取獲得，其製 備方法具體包括以下步驟： 首先，提供一奈米碳管陣列形成於一生長基底，該陣列 爲超順排的奈米碳管陣列。 該奈米碳管陣列採用化學氣相沈積法製備，該奈米碳管 陣列爲多個彼此平行且垂直於生長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，該定 向排列的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，適於從中拉取奈米碳管膜 。本發明實施例提供的奈米碳管陣列爲單壁奈米碳管陣 列、雙壁奈米碳管陣列及多壁奈米碳管陣列中的一種。 所述奈米碳管的直徑爲0.5〜50奈米，長度爲50奈米~5毫 米。本實施例中，奈米碳管的長度優選爲100微米~900微 米。 其次，採用一拉伸工具從所述奈米碳管陣列中拉取奈米 碳管獲得一奈米碳管膜，其具體包括以下步驟：（a)從 所述超順排奈米碳管陣列中選定一個或具有一定寬度的 多個奈米碳管，本實施例優選爲採用具有一定寬度的膠 帶、鑷子或夾子接觸奈米碳管陣列以選定一個或具有一 定寬度的多個奈米碳管；（b)以一定速度拉伸該選定的 奈米碳管，從而形成首尾相連的多個奈米碳管片段，進 098126005 表單編號A0101 第5頁/共33頁 0982044562-0 201103862 而形成一連續的奈米碳管膜。該拉取方向沿基本垂直於 奈米碳管陣列的生長方向。 [0015] 在上述拉伸過程中，該多個奈米碳管片段在拉力作用下 沿拉伸方向逐漸脫離生長基底的同時，由於凡德瓦爾力 作用，該選定的多個奈米碳管片段分別與其它奈米碳管 片段首尾相連地連續地被拉出，從而形成一連續、均勻 且具有一定寬度的自支撑的奈米碳管膜。所謂“自支撑 結構”即該奈米碳管膜無需通過一支撑體支撑，也能保 持一膜的形狀。請參閱圖2，該奈米碳管膜包括多個基本 沿同一方向擇優取向排列且通過凡德瓦爾力首尾相連的 奈米碳管，該奈米碳管基本沿拉伸方向排列並平行於該 奈米碳管膜表面。該直接拉伸獲得奈米碳管膜的方法簡 單快速，適宜進行工業化應用。 [0016] 該奈米碳管膜的寬度與奈米碳管陣列的尺寸有關，該奈 米碳管膜的長度不限，可根據實際需求制得。當該奈米 碳管陣列的面積爲4英寸時，該奈米碳管膜的寬度爲3毫 米〜10厘米，該奈米碳管膜的厚度爲0. 5奈米~1 00微米。 [0017] 可以理解，該奈米碳管膜結構的製備方法可進一步包括 :層叠且交叉鋪設多個所述奈米碳管膜。具體地，可先 將一奈米碳管膜沿一個方向覆蓋至一框架上，再將另一 奈米碳管膜沿另一方向覆蓋至先前的奈米碳管膜表面， 如此反復多次，在該框架上鋪設多個奈米碳管膜。該多 個奈米碳管膜可沿各自不同的方向鋪設，也可僅沿兩個 交叉的方向鋪設。可以理解，該奈米碳管膜結構也爲一 自支撑結構。該奈米碳管膜結構的邊緣通過該框架固定 098126005 表單編號A0101 第6頁/共33頁 0982044562-0 201103862 ，中部懸空設置。 [0018] Ο [0019] 由於該奈米碳管膜具有較大的比表面積，因此該奈米碳 管膜具有較大粘性，故多層奈米碳管膜可相互通過凡德 瓦爾力緊密結合形成一穩定的奈米碳管膜結構。該奈米 碳管膜結構中，奈米碳管膜的層數不限，且相鄰兩層奈 米碳管膜之間具有一交叉角度α，0°<α$90°。本實施 例優選爲α=90°，即該多個奈米碳管膜僅沿兩個相互垂 直的方向相互層叠，奈米碳管膜結構中奈米碳管膜的層 數爲2 - 4層。 形成上述奈米碳管膜結構後，可進一步使用有機溶劑處 理所述奈米碳管膜結構，從而在奈米碳管膜結構中形成 多個微孔。 [0020] ❹ 該有機溶劑爲常溫下易揮發的有機溶劑，可選用乙醇、 甲醇、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 具體爲：通過試管將有機溶劑谪落在形成在所述框架上 的奈米碳管膜結構表面浸潤整個奈米碳管膜結構，或者 ，也可將上述奈米碳管膜結構浸入盛有有機溶劑的容器 中浸潤。請參閱圖3及圖7，所述的奈米碳管膜結構經有 機溶劑浸潤處理後，並排且相鄰的奈米碳管會聚攏，從 而收縮成間隔分布的奈米碳管線，該奈米碳管線包括多 個通過凡德瓦爾力首尾相連的奈米碳管。基本沿相同方 向排列的奈米碳管線之間具有一間隙。由於相鄰兩層奈 米碳管膜中的奈米碳管具有一交叉角度α，且0<α$90° 098126005 表單編號Α0101 第7頁/共33頁 0982044562-0 201103862 ，有機溶劑處理後相鄰兩層奈米碳管膜中的奈米碳管線 相互交叉，從而形成多個微孔。有機溶劑處理後，奈米 碳管膜的粘性降低。該奈米碳管膜結構的微孔的尺寸爲1 奈米~10微米，優選爲1奈米〜900奈米。本實施例中，該 交叉角度α=90°，故該奈米碳管膜結構中的奈米碳管線 基本相互垂直交叉，形成大量微孔。優選地，當該奈米 碳管結構包括四層層叠的奈米碳管膜，該奈米碳管膜結 構中尺寸爲奈米量級的微孔可達到60%以上。可以理解， 該層叠的碳米管膜數量越多，該奈米碳管膜結構的微孔 的尺寸越小。因此，可通過調整該奈米碳管膜的數量得 到需要的微孔尺寸。該微孔的尺寸應小於該石墨烯片的 尺寸，以使一石墨烯片能够完全覆蓋該微孔。可以理解 ，該步驟爲可選擇步驟，當該石墨烯片分散液中的溶劑 爲揮發性有機溶劑時，可通過後續步驟二直接將奈米碳 管膜結構通過該分散液浸潤，達到與本步驟相同的效果 〇 [0021] 該石墨烯片分散液爲將石墨烯片分散於一溶劑中獲得。 本實施例中，該石墨烯片分散液的製備方法具體包括： 提供一定量石墨烯片；將該石墨烯片置入一溶劑中形成 一混合物；超聲振蕩該混合物，使石墨烯片均勻分散並 懸浮在該溶劑中從而獲得一石墨烯片分散液。本實施例 中，該混合物在超聲振蕩儀中振蕩約15分鐘。可以理解 ，還可採用其它方法分散該石墨烯片，如採用機械攪拌 的方法攪拌該石墨烯片與該溶劑的混合物。 [0022] 該溶劑應選擇爲利於石墨烯片分散，且能够完全揮發的 098126005 表單編號Α0101 第8頁/共33頁 0982044562-0 201103862 [0023] θ [0024] [0025] Ο [0026] 低分子量溶劑，如水、乙醇、曱醇、丙_、二氣乙炫和 氣仿中一種或者幾種的混合。本實施例中，該溶劑爲水 。可以理解，該溶劑僅起到均勻分散石墨烯片的作用， 故該溶劑應不與該石墨烯片發生反應，如發生化學反應 或使石墨烯片溶解於溶劑中。 該石墨烯片由單層或多層石墨烯（graphene )組成。優 選地，該石墨烯片分散液中的石墨烯片的層數爲1〜3層， 從而使透射電鏡微栅具有更好的襯度。所述石墨烯爲由 碳原子通過sp2鍵雜化形成的二維片狀結構。該石墨烯片 的尺寸爲10微米以下，可小於1微米。該石墨烯片在該待 測樣品分散液中的濃度爲5% (體積百分含量）以下。 步驟二，將所述石墨烯片分散液浸潤所述奈米碳管膜結 構表面。 該石墨烯片分散液可通過滴管逐滴滴加至上述奈米碳管 膜結構表面，使該奈米碳管膜結構的表面被該石墨烯片 分散液浸潤。可以理解，當該奈米碳管膜結構面積較大 時，可通過其它方式，如將整嗰奈米碳管膜結構整個浸 入所述石墨烯片分散液中，再將該奈米碳管膜結構從石 墨烯片分散液中取出。 本實施例中，採用向鋪設於框架上的奈米碳管膜結構表 面滴加石墨烯片分散液的方式，在框架上形成一被該石 墨烯片分散液浸潤的奈米碳管膜結構。 通過石墨烯片分散液浸潤該奈米碳管膜結構後，可進一 步將另一奈米碳管膜結構覆蓋於上述奈米碳管膜結構通 098126005 表單編號A0101 第9頁/共33頁 0982044562-0 [0027] 201103862 過石墨烯片分散液浸潤的表面，形成一夾心結構。 [0028] 可以理解，該另一奈米碳管膜結構可包括單層或多層奈 米碳管膜，可具有與原奈米碳管膜結構相同或不同的結 構。該步驟可與步驟二重複進行，即形成該夾心結構後 ，進一步將該石墨烯片分散液滴加至該夾心結構表面， 並進一步覆蓋另一奈米碳管膜結構，從而形成一多層夾 心結構。該多層夾心結構包括多層奈米碳管膜結構與多 層石墨稀片分散液相間層叠。本實施例中’該爽心結構 爲兩層奈米碳管膜結構與一層石墨烯片分散液形成的三 層夾心結構。該兩層奈米碳管膜結構夾持中間的石墨烯 片分散液中的石墨烯片，從而使石墨烯片更牢固的固定 。該步驟爲可選擇步驟。 [0029] 步驟三，使該被石墨烯片浸潤的奈米碳管膜結構乾燥， 從而使該石墨烯片與該奈米碳管膜結構複合，形成一石 墨烯片-奈米碳管膜複合結構。 [0030] 當該石墨烯片分散液乾燥後，該奈米碳管膜結構表面形 成一石墨烯片層。該石墨烯片層中的石墨烯片可在奈米 碳管膜結構表面連續或離散的分布，視石墨烯片分散液 的滴加次數及濃度而定。請參閱圖7，該石墨烯片-奈米 碳管膜複合結構中，至少一石墨烯片覆蓋該奈米碳管膜 結構中至少一微孔。 [0031] 當形成三層夾心結構時，兩層奈米碳管膜結構中的奈米 碳管夾持該石墨烯片層中的石墨烯片，從而使該石墨烯 片更穩定的固定在該三層夾心結構中。 098126005 表單編號A0101 第10頁/共33頁 201103862 [0032] [0033] Ο [0034] 形成所述石墨烯片-奈米碳管膜複合結構後，可進一步處 理該石墨烯片-奈米碳管膜複合結構，使該石墨烯片與該 奈米碳管膜中的奈米碳管鍵合連接。 該處理步驟具體可爲通過激光或紫外光照射該石墨烯片-奈米碳管膜複合結構；或通過高能粒子（high-energy particle)轟擊該石墨浠片-奈米碳管膜複合結構。經處 理後，該石墨烯片中的碳原子與奈米碳管中的碳原子通 過sp3雜化形成共價鍵連接，從而使石墨烯片更穩定的固 定於該奈米碳管膜結構表面》該步驟爲可選擇步驟，當 本方法不包括該步驟時，該石墨烯片通過凡德瓦爾力與 該奈米碳管結合。 步驟四，將所述石墨烯片-奈米碳管膜複合結構覆蓋一金 屬網格。 [0035] [0036] 該金屬網格具有至少一通孔，該石墨烯片-奈米碳管膜複 合結構覆蓋該通孔的部分懸空設置。 當該石墨烯片-奈米碳管膜複合結構面積較大時，可進一 步包括：將多個金屬網格間隔排列；將該石墨烯片-奈米 碳管膜複合結構整個覆蓋該多個金屬網格；以及從相鄰 的兩個金屬網格之間斷開該石墨烯片-奈米碳管膜複合結 構，從而一次性形成多個表面覆蓋有石墨烯片-奈米碳管 膜複合結構的金屬網格。 具體地，可採用激光束聚焦照射兩相鄰的金屬網格之間 ，燒斷該石墨烯片-奈米碳管膜複合結構。本實施例中， 該激光束功率爲5〜30瓦（W)，優選爲18W。 098126005 表單編號A0101 第11頁/共33頁 0982044562-0 [0037] 201103862 [0038] [0039] [0040] 進一步地，可使用有機溶劑處理覆蓋在金屬網格上的石 墨烯片-奈米碳管膜複合結構，使該石墨烯片-奈米碳管 膜複合結構和金屬網格結合緊密，並沿金屬網格邊沿去 除多餘的石墨烯片-奈米碳管膜複合結構’即製成透射電 鏡微栖β 上述有機溶劑爲常溫下易揮發的有機溶劑，如乙醇、甲 醇、丙鲷、二氯乙烷或氯仿，本實施例中採用乙醇。該 有機溶劑可直接滴在石墨烯片—奈米碳管膜複合結構表面 ’使s玄石墨稀片-奈米碳管膜複合結構和金屬網格結合緊 密。另’可將上述覆袁有石墨烯片-奈米碳管膜複合結構 的金屬網格整個浸入盛有有機溶劑的容;器中浸潤。該去 除金屬網格以外多餘的石墨烯片-奈米碳管膜複合結構的 步驟可爲通過一激光束聚焦，並沿該金屬網格邊沿照射 一周，燒蝕該石墨烯片-奈米碳管膜複合結構，從而去除 金屬網格外多餘的石墨烯片-奈米碳管膜複合結構。該步 二 .. 驟爲可選擇步驟。 本發明實施例所提供的透射電鏡懲栅的製備方法具有以 下優點。首先，由於奈米破管膜及由奈米破管膜形成的 奈米碳管膜結構具有自支撑性’可方便地鋪設及層叠， 另，也可方便地將一奈米碳管膜結構覆蓋在另一表面具 有石墨烯片的奈米碳管媒結構上’使兩奈米碳管膜結構 夹持其間的石墨烯片。其次，該採用激光、紫外光或高 能粒子處理該石墨烯片-奈米碳管膜複合結構的方法可使 該石墨烯片與奈米碳管祺通過共價鍵更牢固地結合°再 次，由於該奈米碳管膜結構具有極大的比表面積’因此 098126005 表單編號Α0101 第12賓/共33頁 0982044562-0 201103862 [0041] Ο [0042] [0043] 〇 具有較大粘性，可良好的粘附於所述金屬網格上，通過 有機溶劑處理，該奈米碳管膜結構與該金屬網格的結合 更爲牢固。進一步地，所述石墨烯片-奈米碳管膜結構可 一次覆蓋在多個金屬網格上，方法簡單、快捷，通過去 除金屬網格以外的石墨烯片-奈米碳管膜結構，可批量製 備性質穩定的透射電鏡微栅。 請參閱圖4，圖5及圖7，本發明提供一種透射電鏡微栅 100，其包括一金屬網格110及覆蓋在金屬網格110表面 的一石墨烯片-奈米碳管膜複合結構120。 該石墨烯片-奈米碳管膜複合結構120包括至少一奈米碳 管膜結構122及多個石墨烯片124設置於該奈米碳管膜結 構122表面。該奈米碳管膜結構122包括多個微孔126， 其中，至少一微孔126被一石墨烯片124覆蓋。 具體地，請一並參閱圖2及圖3，該奈米碳管膜結構122包 括多層奈米碳管膜層叠設置。該奈米碳管由爲從一奈米 碳管陣列拉取獲得，包括多個基本沿同一方向擇優取向 且平行於奈米碳管膜表面排列的奈米碳管。所述奈米碳 管通過凡德瓦爾力首尾相連。該奈米碳管膜結構122中多 層奈米碳管膜相互交叉且層叠設置。由於每層奈米碳管 膜中，奈米碳管沿一個方向擇優取向排列，因此，相鄰 兩層奈米碳管膜中的奈米碳管間具有一交叉角度α，0°< α $90°。本實施例優選爲α=90°。 請參閱圖5及圖7，該奈米碳管結構122包括多個交叉的奈 米碳管線128，該奈米碳管線128包括並排且通過凡德瓦 098126005 表單編號Α0101 第13頁/共33·頁 0982044562-0 [0044] 201103862 爾力聚攏的奈米碳管，進一步地，該奈米碳管線128包括 通過凡德瓦爾力首尾相連且基本沿同一方向擇優取向排 列的奈米碳管。該交叉的奈米碳管線128在該奈米碳管膜 、、、α構1 2 2中疋義多個微孔1 2 6。該奈米碳管膜結構1 2 2的 微孔126的尺寸與奈米碳管膜的層數有關。該奈米碳管膜 結構122中奈米碳管膜的層數不限，優選爲2~4層。該奈 米碳管膜結構122中微孔126的尺寸可爲1奈米〜丨微米， 優選地，100奈米以下的微孔可達到6〇%以上。 [0045] [0046] [0047] 該石墨烯片124包括一層或多層石墨稀，該石墨烯片124 的尺寸大於該奈米碳管膜結構122中微孔126的尺寸，並 完全覆蓋該微孔126。該石墨稀月124的尺寸爲2奈米〜1〇 微米。優選地，該石墨烯片的尺寸爲2奈米〜丨微米。本實 施例中，該石墨烯片124包括1層~3層石墨烯。 進一步地，該石墨烯片124中的碳原子與該奈米碳管中的 碳原子可通過sp3雜化鍵合ί，從刼使譚石墨烯片124穩定 的固定於該奈米碳管膜結構122上〇 進一步地，S亥石墨稀片-奈米碳管膜複合結構120可包括 多個奈米碳管膜結構122層叠設置及多個石墨烯片124設 置於相鄰的兩奈米碳管膜結構丨22之間。請參閱圖6，該 石墨烯片124可設置於兩奈米碳管膜結構丨22之間，被兩 奈米碳管膜結構122中的奈米碳管線128夾持，從而使該 石墨烯片124穩定的固定於該奈米碳管膜結構丨22上。 該金屬網格110爲一形成有一個或多個通孔112的金屬片 。該金屬網格110可爲一透射電鏡用金屬網格11〇。該金 098126005 表單編號Α0101 第14頁/共33頁 0982044562-0 [0048] 201103862 Ο [0049] [0050] 〇 [0051] [0052] 屬網格ιιο的材料爲銅或其他金屬材料。該石墨烯片-齐 米碳管膜複合結構12〇基本覆蓋該金屬網格11〇，從而使 該石墨烯片-奈米碳管膜複合結構12〇能够通過該金屬網 格110部分懸空設置，本實施例中，該石墨烯片_奈米碳 管膜複合結構120具有與該金屬網格11〇相等的面積及形 狀，並元全覆蓋§亥金屬網格110的所有通孔112。另，該 金屬網格110的通孔U 2的孔徑遠大於奈米碳管膜結構 122具有的微孔126的尺寸，且大於該石墨烯片124的尺 寸。本實施例中，該金屬網格的通孔112的直徑爲1〇微米 〜2 可以理解，該透射電鏡微栅1〇〇也可採用其他材料（如陶 瓷）製成的網格代替該金屬網格110。 本實施例透射電鏡微栅100在應用時，待觀察的樣品2〇〇 被設置於該透射電鏡微栅1〇〇表面。具體地，請參閱圖8 及圖9，該樣品200設置於覆蓋該奈米碳管膜結構丨22的微 孔126的石墨烯片124表面p該樣品2〇〇可爲奈米顆粒， 如奈米線、奈米球或奈米管等。該樣品2〇〇的尺寸可小於 1微米，優選爲10奈米以下。請參閱圖9及圖1〇,其爲將 一奈来金分散液滴加至上述透射電鏡微栅1〇〇的表面，乾 燥後在透射電鏡下觀察得到的不同分辨率的透射電鏡照 片。圖中黑色顆粒爲待觀察的奈米金顆粒。 本發明實施例提供的透射電鏡微栅1〇〇具有以下優點。 首先，該石墨烯片124起承載樣品2〇〇作用，大量樣品 200可均勻分布於石墨烯片ι24表面可用於測量樣品 098126005 表單編號A0101 第15頁/共33頁 0982044562-0 201103862 2 0 0粒控的統計分布，以及觀察該大量樣品2 〇 〇在石墨烯 片表面的自組裝特性。由於該石墨烯片124覆蓋該微孔 126 ’該樣品200可被該石墨烯片124承載，從而均勻分 布於該奈米碳管臈結構122的微孔丨26上方，從而提高了 該透射電鏡微栅1〇〇對樣品的承載概率。並且，該待測樣 品200的粒徑不受限制，例如僅比該微孔126稍小。 [0053] [0054] [0055] 其入，製備大尺寸的石墨烯片124較爲困難，以先前的方 法製備的石墨烯片124的尺寸小於10微米，因此，由於奈 米碳管膜結構122具有奈求級微孔m (尺寸在i奈米以^ ，且小於1微米），故該石墨焊片124的尺寸無須太大， 也可完全覆蓋該微孔126，從而使該微栅1〇〇可用於觀察 的有效面積達到最大，避免了由於微孔過大，造成石墨 烯片124無法完全覆蓋微孔的情况。 1π^丹有極溥的厚度，單層石墨烯的厚度 約〇. 335奈米，在透射電鏡觀察中產生祕度噪聲較小， 從而可獲縣辨率更㈣透射電鏡照片。另，具有小直 徑（如2微米以下）通孔的金屬網格必須通過 複雜且高成本工藝製備。而太宭/匕 一 费褽備而本實施例中，該金屬網格11〇 的孔徑無需很小，因此該金屬網袼UG的成本大大降低。 第四’由於用於從奈米碳管陣列中拉取獲得的奈米碳管 膜純淨度高，無需通過熱處理去_f。該拉取製備太 米碳管膜时法簡單，有利於降低該透射電鏡微棚^ 成本。本實施例透射電鏡微栅1G對承載於其上的待 樣品的形鮮結構分料顿小，對奈米難樣 分辨像影響报小。 ^ 098126005 表單編號A0101 第16頁/共33頁 0982044562- 201103862 [0056] 進一步地，由於奈米碳管膜結構122及石墨烯片124均由 碳原子鍵合形成，且具有相似的結構，故該奈米碳管膜 結構12 2與石墨稀片12 4具有良好的匹配性，可通過處理 形成sp3共價鍵，從而形成一體結構，便於使用或長時間 保存。 [0057] 另，該石墨烯片-奈米碳管膜複合結構120可包括至少兩 奈米碳管膜結構122 ’並夾持設置於該兩石墨烯片-奈米 碳管膜複合結構120之間的石墨烯片124。此種結構可使 〇 該透射電鏡微栅1〇〇具有更穩定的結構，便於重複使用或 長時間保存。 [0058] 本領域技術人員可以理解，上述石墨烯片及奈米碳管膜 結構中的微孔均爲矩形或不規則多邊形結構，上述該石 墨烯片的尺寸均指從該石墨烯片邊緣一點到另一點的最 大直線距離，該微孔的尺寸均指從該微孔内一點到另一 點的最大直線距離。 [0059] 综上所述，本發明確已符合發明專利之要件，遂依法提 〇 出專利申請β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】 [0060] 圖1爲本發明實施例透射電鏡微栅的製備方法的流程示意 圖。 .[0008] [Embodiment] The present invention will be described in conjunction with the present invention. [0009] Please refer to FIG. 1, the present day is assuming that the preparation method of the first embodiment TEM microgrid mainly includes the following Step: Method 098126005 Form No. 1010101 Page 4 of 33 〇982〇44562~〇201103862 [0011] [0012] [0013] [0014] Step one, providing a carbon nanotube film structure, And a graphene sheet dispersion. The carbon nanotube membrane structure comprises a plurality of layers of cross-laminated carbon nanotube membranes. The carbon nanotube film is obtained by directly drawing from a carbon nanotube array, and the preparation method comprises the following steps: First, providing a carbon nanotube array formed on a growth substrate, the array is super-aligned Nano carbon tube array. The carbon nanotube array is prepared by chemical vapor deposition, and the carbon nanotube array is a plurality of pure carbon nanotube arrays formed of carbon nanotubes which are parallel to each other and perpendicular to the growth substrate. By the above-mentioned controlled growth conditions, the aligned carbon nanotube array contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles, and is suitable for pulling a carbon nanotube film therefrom. The carbon nanotube array provided by the embodiment of the invention is one of a single-walled carbon nanotube array, a double-walled carbon nanotube array, and a multi-walled carbon nanotube array. The carbon nanotubes have a diameter of 0.5 to 50 nm and a length of 50 nm to 5 mm. In this embodiment, the length of the carbon nanotubes is preferably from 100 μm to 900 μm. Next, a carbon nanotube film is obtained by pulling a carbon nanotube from the carbon nanotube array using a stretching tool, which specifically includes the following steps: (a) from the super-shoring carbon nanotube array One of the plurality of carbon nanotubes having a certain width or a certain width is selected. In this embodiment, it is preferable to contact the carbon nanotube array with a tape, a tweezers or a clip having a certain width to select one or a plurality of carbon nanotubes having a certain width. (b) stretching the selected carbon nanotubes at a certain speed to form a plurality of carbon nanotube segments connected end to end, forming a continuous shape in 098126005 Form No. A0101 Page 5 of 33 098204456-2-0 201103862 Nano carbon tube membrane. The pull direction is substantially perpendicular to the growth direction of the nanotube array. [0015] In the above stretching process, the plurality of carbon nanotube segments are gradually separated from the growth substrate in the stretching direction under the tensile force, and the selected plurality of carbon nanotube segments are affected by the van der Waals force. They are continuously drawn end-to-end with other carbon nanotube segments, respectively, to form a continuous, uniform and self-supporting carbon nanotube film having a certain width. The so-called "self-supporting structure" means that the carbon nanotube film can maintain the shape of a film without being supported by a support. Referring to FIG. 2, the carbon nanotube film comprises a plurality of carbon nanotubes arranged in a preferred orientation in the same direction and connected end to end by a van der Waals force, the carbon nanotubes being arranged substantially in the stretching direction and parallel to the Nano carbon tube membrane surface. The direct stretching method for obtaining a carbon nanotube film is simple and rapid, and is suitable for industrial application. [0016] The width of the carbon nanotube film is related to the size of the carbon nanotube array, and the length of the carbon nanotube film is not limited and can be obtained according to actual needs. 5纳米至1 00微米。 The carbon nanotube film has a thickness of from 0. 5 nm to 1 00 μm. The carbon nanotube film has a thickness of from 0.5 mm to 10 cm. [0017] It can be understood that the method for preparing the carbon nanotube film structure may further include: laminating and cross laying a plurality of the carbon nanotube films. Specifically, a carbon nanotube film may be first covered in one direction to one frame, and another carbon nanotube film may be covered in another direction to the surface of the previous carbon nanotube film, and thus repeated, A plurality of carbon nanotube membranes are laid on the frame. The plurality of carbon nanotube membranes may be laid in different directions or may be laid only in two intersecting directions. It will be understood that the carbon nanotube membrane structure is also a self-supporting structure. The edge of the carbon nanotube membrane structure is fixed by the frame 098126005 Form No. A0101 Page 6 of 33 0982044562-0 201103862 , the central suspension setting. [0019] Since the carbon nanotube film has a large specific surface area, the carbon nanotube film has a large viscosity, so that the multilayer carbon nanotube film can be closely combined with each other by van der Waals force. A stable carbon nanotube membrane structure. In the carbon nanotube film structure, the number of layers of the carbon nanotube film is not limited, and the adjacent two layers of carbon nanotube film have an intersection angle α, 0° < α $ 90 °. This embodiment is preferably α=90°, that is, the plurality of carbon nanotube films are stacked on each other only in two mutually perpendicular directions, and the number of layers of the carbon nanotube film in the carbon nanotube film structure is 2 - 4 layers. . After the above-described carbon nanotube film structure is formed, the carbon nanotube film structure can be further treated with an organic solvent to form a plurality of micropores in the carbon nanotube film structure. [0020] 有机 The organic solvent is a volatile organic solvent at normal temperature, and one or a mixture of ethanol, methanol, acetone, di-ethane and gas may be used. The organic solvent in this embodiment is ethanol. The organic solvent should have good wettability with the carbon nanotubes. The step of treating with an organic solvent is specifically: infiltrating the organic solvent onto the surface of the carbon nanotube film structure formed on the frame by a test tube to infiltrate the entire carbon nanotube film structure, or the above-mentioned nano carbon can also be used. The tubular membrane structure is immersed in a container containing an organic solvent to infiltrate. Referring to FIG. 3 and FIG. 7 , after the carbon nanotube membrane structure is infiltrated by an organic solvent, the adjacent carbon nanotubes are gathered side by side and contracted into a nano carbon line with a spacing distribution, the nanometer. The carbon pipeline consists of a number of carbon nanotubes connected end to end by Van der Valli. There is a gap between the nanocarbon lines arranged substantially in the same direction. Since the carbon nanotubes in the adjacent two layers of carbon nanotube film have a crossing angle α, and 0 < α $ 90 ° 098126005 Form No. 101 0101 Page 7 / Total 33 pages 098204456-2-0 201103862, adjacent to the organic solvent treatment The nanocarbon lines in the two-layer carbon nanotube film cross each other to form a plurality of micropores. After the organic solvent treatment, the viscosity of the carbon nanotube film is lowered. The size of the micropores of the carbon nanotube membrane structure is from 1 nm to 10 μm, preferably from 1 nm to 900 nm. In this embodiment, the intersection angle α = 90°, so that the nanocarbon pipelines in the carbon nanotube membrane structure substantially cross each other perpendicularly to form a large number of micropores. Preferably, when the carbon nanotube structure comprises four stacked carbon nanotube membranes, the pore size of the nanocarbon membrane structure can be more than 60%. It can be understood that the larger the number of the laminated carbon nanotube film, the smaller the size of the micropores of the carbon nanotube film structure. Therefore, the desired pore size can be obtained by adjusting the number of the carbon nanotube membranes. The size of the micropores should be smaller than the size of the graphene sheet so that a graphene sheet can completely cover the micropores. It can be understood that the step is an optional step. When the solvent in the graphene sheet dispersion is a volatile organic solvent, the carbon nanotube membrane structure can be directly infiltrated through the dispersion through the subsequent step 2, and the step is achieved. The same effect [0021] The graphene sheet dispersion is obtained by dispersing a graphene sheet in a solvent. In this embodiment, the method for preparing the graphene sheet dispersion comprises: providing a certain amount of graphene sheets; placing the graphene sheets in a solvent to form a mixture; ultrasonically shaking the mixture to uniformly disperse the graphene sheets and It is suspended in the solvent to obtain a graphene sheet dispersion. In this example, the mixture was shaken in an ultrasonic shaker for about 15 minutes. It will be appreciated that the graphene sheet may also be dispersed by other methods, such as stirring the mixture of the graphene sheet and the solvent by mechanical agitation. [0022] The solvent should be selected to facilitate the dispersion of graphene sheets, and can be completely volatilized 098126005 Form No. 101 0101 Page 8 / Total 33 pages 0982044562-0 201103862 [0023] θ [0024] [0025] 0026 [0026] Low molecular weight A solvent, such as a mixture of one or more of water, ethanol, methanol, propylene, dioxane, and gas. In this embodiment, the solvent is water. It is understood that the solvent acts only to uniformly disperse the graphene sheet, so the solvent should not react with the graphene sheet, such as a chemical reaction or dissolution of the graphene sheet in a solvent. The graphene sheet is composed of a single layer or a plurality of graphenes. Preferably, the number of layers of the graphene sheets in the graphene sheet dispersion is from 1 to 3 layers, so that the transmission electron micro-gate has a better contrast. The graphene is a two-dimensional sheet-like structure formed by carbon atom fusion by sp2 bonding. The graphene sheet has a size of 10 μm or less and may be less than 1 μm. The graphene sheet has a concentration of 5% (volume percentage) or less in the dispersion of the sample to be tested. In step two, the graphene sheet dispersion is impregnated onto the surface of the carbon nanotube film structure. The graphene sheet dispersion can be dropwise added to the surface of the above-mentioned carbon nanotube film structure through a dropper so that the surface of the carbon nanotube film structure is wetted by the graphene sheet dispersion. It can be understood that when the structure area of the carbon nanotube film is large, the carbon nanotube film can be further immersed in the graphene sheet dispersion by other means, such as immersing the entire carbon nanotube film structure. The structure was taken out from the graphene sheet dispersion. In the present embodiment, a carbon nanotube film structure infiltrated with the dispersion of the graphene sheet is formed on the frame by dropping a graphene sheet dispersion onto the surface of the carbon nanotube film structure laid on the frame. After infiltrating the carbon nanotube film structure by the graphene sheet dispersion, another carbon nanotube film structure can be further covered by the above-mentioned carbon nanotube film structure. 098126005 Form No. A0101 Page 9 of 33 0982044562- 0 [0027] 201103862 Over the surface of the graphene sheet dispersion infiltrated to form a sandwich structure. It is to be understood that the other carbon nanotube membrane structure may comprise a single or multiple carbon nanotube membrane, and may have the same or different structure as the original carbon nanotube membrane structure. This step may be repeated with the second step, that is, after the sandwich structure is formed, the graphene sheet dispersion droplet is further added to the surface of the sandwich structure, and further covers another carbon nanotube film structure to form a multilayer sandwich. structure. The multilayer sandwich structure comprises a multilayered carbon nanotube film structure laminated with a plurality of layers of graphite flakes. In the present embodiment, the refreshing structure is a three-layer sandwich structure formed by a two-layer carbon nanotube film structure and a layer of graphene sheet dispersion. The two-layered carbon nanotube film structure holds the graphene sheets in the intermediate graphene sheet dispersion, thereby making the graphene sheets more firmly fixed. This step is an optional step. [0029] Step 3, drying the carbon nanotube film structure infiltrated by the graphene sheet, so that the graphene sheet and the carbon nanotube film structure are combined to form a graphene sheet-nanocarbon tube film composite structure. [0030] When the graphene sheet dispersion is dried, the surface of the carbon nanotube film structure forms a graphene sheet. The graphene sheets in the graphene sheets may be continuously or discretely distributed on the surface of the carbon nanotube film structure, depending on the number and concentration of the graphene sheet dispersion. Referring to FIG. 7, in the graphene sheet-nano carbon tube film composite structure, at least one graphene sheet covers at least one micropores in the carbon nanotube film structure. [0031] When a three-layer sandwich structure is formed, a carbon nanotube in the two-layer carbon nanotube film structure sandwiches a graphene sheet in the graphene sheet layer, thereby fixing the graphene sheet more stably in the Three-layer sandwich structure. 098126005 Form No. A0101 Page 10 / Total 33 Page 201103862 [0033] After forming the graphene sheet-nanocarbon tube film composite structure, the graphene sheet-carbon nanotube can be further processed The film composite structure is such that the graphene sheet is bonded to the carbon nanotube in the carbon nanotube film. The processing step may specifically be irradiating the graphene sheet-nanocarbon tube film composite structure by laser or ultraviolet light; or bombarding the graphite sheet-nano carbon tube film composite structure by high-energy particles. After the treatment, the carbon atoms in the graphene sheet are covalently bonded to the carbon atoms in the carbon nanotube by sp3 hybridization, thereby making the graphene sheet more stably fixed on the surface of the carbon nanotube membrane structure. This step is an optional step, and when the method does not include the step, the graphene sheet is bonded to the carbon nanotube by a van der Waals force. In step four, the graphene sheet-nanocarbon tube film composite structure is covered with a metal mesh. [0036] The metal mesh has at least one through hole, and the graphene sheet-carbon nanotube film composite structure covers a partially suspended arrangement of the through hole. When the graphene sheet-nanocarbon tube film composite structure has a large area, the method further includes: spacing a plurality of metal grids; and covering the plurality of metals with the graphene sheet-nanocarbon tube film composite structure Grid; and disconnecting the graphene sheet-nanocarbon tube film composite structure from two adjacent metal grids, thereby forming a plurality of surfaces covered with a graphene sheet-nanocarbon tube film composite structure at one time Metal grid. Specifically, a laser beam can be used to focus and illuminate between two adjacent metal meshes, and the graphene sheet-carbon nanotube film composite structure is blown. In this embodiment, the laser beam power is 5 to 30 watts (W), preferably 18 W. 098126005 Form No. A0101 Page 11 / Total 33 Page 0982044562-0 [0037] [0040] Further, the graphene sheet-nanocarbon tube covering the metal grid can be treated with an organic solvent. The film composite structure makes the graphene sheet-nanocarbon tube film composite structure and the metal mesh tightly combined, and removes excess graphene sheet-nano carbon tube film composite structure along the edge of the metal grid to form a transmission electron microscope. Micro-inorganic β The above organic solvent is an organic solvent which is volatile at normal temperature, such as ethanol, methanol, propanil, dichloroethane or chloroform, and ethanol is used in this embodiment. The organic solvent can be directly dropped on the surface of the graphene sheet-nanocarbon tube membrane composite structure to make the s-graphite-small-small carbon nanotube film composite structure and the metal mesh tightly combined. Alternatively, the metal mesh of the above graphene-graphene-carbon nanotube film composite structure may be entirely immersed in a container containing an organic solvent; The step of removing the excess graphene sheet-nanocarbon tube film composite structure other than the metal grid may be performed by focusing a laser beam and irradiating the edge of the metal grid for one week to ablate the graphene sheet-carbon nanotube The membrane composite structure removes excess graphene sheet-nanocarbon tube membrane composite structure outside the metal grid. Step 2: The step is an optional step. The preparation method of the transmission electron microscope correction gate provided by the embodiment of the invention has the following advantages. First, since the nano-tube membrane and the nano-carbon tube membrane structure formed by the nano-tube membrane are self-supporting, they can be conveniently laid and laminated, and it is also convenient to cover a carbon nanotube membrane structure. The other surface of the carbon nanotube medium having a graphene sheet has a graphene sheet sandwiching the two carbon nanotube film structure therebetween. Secondly, the method for treating the graphene sheet-nanocarbon tube film composite structure by using laser, ultraviolet light or high-energy particles can make the graphene sheet and the carbon nanotubes are more firmly bonded by a covalent bond. The carbon nanotube membrane structure has a very large specific surface area 'so 098126005 Form No. Α0101 12th/Total 33 Page 0982044562-0 201103862 [0041] [0043] 〇 has a large viscosity and can adhere well On the metal grid, the carbon nanotube film structure is more firmly bonded to the metal mesh by organic solvent treatment. Further, the graphene sheet-nanocarbon tube membrane structure can be covered on a plurality of metal grids at one time, and the method is simple and quick, and the graphene sheet-nanocarbon tube membrane structure other than the metal grid can be removed. A TEM microgrid with stable properties was prepared in batches. Referring to FIG. 4 , FIG. 5 and FIG. 7 , the present invention provides a TEM micro-gate 100 comprising a metal mesh 110 and a graphene sheet-carbon nanotube film composite structure 120 covering the surface of the metal mesh 110 . . The graphene sheet-nanocarbon tube film composite structure 120 includes at least one carbon nanotube film structure 122 and a plurality of graphene sheets 124 disposed on the surface of the carbon nanotube film structure 122. The carbon nanotube membrane structure 122 includes a plurality of micropores 126, wherein at least one of the micropores 126 is covered by a graphene sheet 124. Specifically, referring to Figures 2 and 3 together, the carbon nanotube membrane structure 122 includes a multilayer carbon nanotube membrane laminate arrangement. The carbon nanotubes are obtained by drawing from a carbon nanotube array, and include a plurality of carbon nanotubes which are oriented substantially in the same direction and aligned parallel to the surface of the carbon nanotube film. The carbon nanotubes are connected end to end by Van der Waals force. The plurality of carbon nanotube films in the carbon nanotube film structure 122 are interdigitated and laminated. Since each of the carbon nanotube membranes is arranged in a preferred orientation in one direction, the carbon nanotubes in the adjacent two carbon nanotube membranes have an intersection angle α, 0° < α $90°. This embodiment is preferably α = 90°. Referring to Figures 5 and 7, the carbon nanotube structure 122 includes a plurality of intersecting nanocarbon lines 128 including side-by-side and through Van der Waals 098126005 Form No. 1010101 Page 13 of 33 Page 0982044562-0 [0044] 201103862 The carbon nanotubes gathered by Erli, further, the nanocarbon pipeline 128 comprises carbon nanotubes arranged end to end by van der Waals force and arranged in a preferred orientation substantially in the same direction. The intersecting nanocarbon line 128 has a plurality of micropores 1 2 6 in the carbon nanotube membrane, α, and 1 2 2 . The size of the micropores 126 of the carbon nanotube film structure 1 2 2 is related to the number of layers of the carbon nanotube film. The number of layers of the carbon nanotube film in the carbon nanotube film structure 122 is not limited, and is preferably 2 to 4 layers. The size of the micropores 126 in the carbon nanotube membrane structure 122 may range from 1 nm to 丨 micrometers, and preferably, the micropores of 100 nm or less may reach 6 % or more. [0047] The graphene sheet 124 includes one or more layers of graphite thinner having a size larger than the size of the micropores 126 in the carbon nanotube membrane structure 122 and completely covering the micropores. 126. The size of the graphite thin moon 124 is 2 nm to 1 μm. Preferably, the graphene sheet has a size of 2 nm to 丨 micron. In the present embodiment, the graphene sheet 124 includes one to three layers of graphene. Further, the carbon atoms in the graphene sheet 124 and the carbon atoms in the carbon nanotubes can be bonded by sp3 hybridization, and the tan graphene sheet 124 is stably fixed to the carbon nanotube membrane structure from the crucible. Further, the S-Heil graphite thin film-nano carbon tube film composite structure 120 may include a plurality of carbon nanotube film structures 122 stacked and a plurality of graphene sheets 124 disposed on adjacent two carbon nanotubes. The membrane structure is between the crucibles 22. Referring to FIG. 6, the graphene sheet 124 may be disposed between the two carbon nanotube film structures 丨22 and sandwiched by the nano carbon line 128 in the two carbon nanotube film structure 122, thereby making the graphene sheet 124 is stably attached to the carbon nanotube membrane structure 22. The metal mesh 110 is a metal piece formed with one or more through holes 112. The metal mesh 110 can be a metal mesh 11 透射 for transmission electron mirrors. The gold 098126005 Form No. Α0101 Page 14 of 33 0982044562-0 [0048] [0050] [0052] The material of the mesh ιιο is copper or other metal material. The graphene sheet-zomi carbon nanotube film composite structure 12〇 substantially covers the metal grid 11〇, so that the graphene sheet-nanocarbon tube film composite structure 12〇 can be partially suspended by the metal grid 110, In this embodiment, the graphene sheet-carbon nanotube film composite structure 120 has the same area and shape as the metal grid 11〇, and covers all the through holes 112 of the metal grid 110. In addition, the aperture of the through hole U 2 of the metal mesh 110 is much larger than the size of the micropores 126 of the carbon nanotube film structure 122 and larger than the size of the graphene sheet 124. In this embodiment, the diameter of the through hole 112 of the metal mesh is 1 〇 micrometer 〜2. It can be understood that the TEM micro ridge 1 〇〇 can also be replaced by a mesh made of other materials (such as ceramic). Grid 110. In the embodiment, the TEM micro-gate 100 is applied, and the sample 2 待 to be observed is disposed on the surface of the TEM micro-gate 1 . Specifically, referring to FIG. 8 and FIG. 9, the sample 200 is disposed on the surface of the graphene sheet 124 covering the micropores 126 of the carbon nanotube membrane structure 22, and the sample 2 can be a nanoparticle, such as Nai. Rice noodles, nano balls or nanotubes. The sample 2〇〇 may have a size of less than 1 μm, preferably 10 nm or less. Referring to FIG. 9 and FIG. 1A, a neat gold dispersion droplet is applied to the surface of the TEM micro-gate 1 ,, and after drying, a TEM image of different resolutions observed under a transmission electron microscope is observed. The black particles in the figure are the nano gold particles to be observed. The TEM micro-gate 1 本 provided by the embodiment of the invention has the following advantages. First, the graphene sheet 124 functions as a sample carrying material, and a large amount of sample 200 can be uniformly distributed on the surface of the graphene sheet ι24 for measurement of sample 098126005. Form No. A0101 Page 15 of 33 0982044562-0 201103862 2 0 0 The statistical distribution of the control, as well as the self-assembly characteristics of the large amount of sample 2 on the surface of the graphene sheet. Since the graphene sheet 124 covers the micropores 126', the sample 200 can be carried by the graphene sheets 124 to be evenly distributed over the micropores 26 of the carbon nanotube structure 122, thereby improving the transmission electron microscopy. The probability of carrying the grid to the sample. Further, the particle size of the sample to be tested 200 is not limited, for example, only slightly smaller than the micropores 126. [0055] It is difficult to prepare a large-sized graphene sheet 124, and the size of the graphene sheet 124 prepared by the prior method is less than 10 μm, and therefore, due to the carbon nanotube film structure 122 The micro-hole m has a size of n (the size is in the range of i nanometer and less than 1 micrometer), so the size of the graphite soldering piece 124 does not need to be too large, and the micro-hole 126 can be completely covered, so that the micro-gate 1〇 The effective area that can be used for observation is maximized, and the case where the graphene sheet 124 cannot completely cover the micropores due to the excessive micropores is avoided. 1π^ Dan has a very thick thickness, the thickness of single-layer graphene is about 335. 335 nm, the secret noise is less in the transmission electron microscope observation, so that the county can be more accurate (four) transmission electron micrograph. In addition, metal grids with small diameters (e.g., below 2 microns) must be fabricated through a complex and costly process. However, in this embodiment, the aperture of the metal mesh 11〇 does not need to be small, so the cost of the metal mesh UG is greatly reduced. Fourthly, since the carbon nanotube film obtained for drawing from the carbon nanotube array has high purity, it is not necessary to remove _f by heat treatment. The method for preparing the carbon nanotube film is simple, and is advantageous for reducing the cost of the TEM microcavity. In the embodiment, the TEM microgrid 1G has a small amount of the fresh structure of the sample to be carried thereon, and has a small influence on the resolution of the nanometer image. ^ 098126005 Form No. A0101 Page 16 of 33 0982044562- 201103862 Further, since the carbon nanotube film structure 122 and the graphene sheet 124 are both formed by carbon atom bonding and have a similar structure, The carbon nanotube film structure 12 2 has good compatibility with the graphite flakes 12 4 , and can form a sp3 covalent bond by treatment, thereby forming an integral structure, which is convenient for use or long-term storage. [0057] In addition, the graphene sheet-nanocarbon tube film composite structure 120 may include at least two carbon nanotube film structures 122' and is sandwiched and disposed on the two graphene sheet-carbon nanotube film composite structures 120. Inter-graphene sheet 124. This structure allows the TEM microgrid 1 to have a more stable structure for re-use or long-term storage. [0058] It can be understood by those skilled in the art that the micropores in the graphene sheet and the carbon nanotube film structure are rectangular or irregular polygonal structures, and the size of the graphene sheet refers to a point from the edge of the graphene sheet. The maximum linear distance to another point, the size of the micro-hole refers to the maximum linear distance from one point to another point in the micro-hole. [0059] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is legally extracted. However, the above description is only a preferred embodiment of the present invention, and the application of the case cannot be limited thereby. Patent scope. 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 [0060] FIG. 1 is a flow chart showing a method of fabricating a TEM microgate according to an embodiment of the present invention. .
[0061] 圖2爲本發明實施例透射電鏡微栅中的奈米碳管膜的掃描 098126005 表單編號Α0101 第17賓/共33頁 0982044562-0 201103862 電鏡照片。 [0062] [0063] [0064] [0065] [0066] [0067] [0068] [0069] [0070] 圖3爲本發明實施例透射電鏡微栅中由多層交叉的奈米碳 營膜形成的奈米碳管膜結構的掃描電鏡照片。 圖4爲本發明實施例透射電鏡微栅的結構示意圖。 圖5爲本發明實施例透射電鏡微栅中一種石墨烯片-奈米 碳管骐結構的結構示意圖。 圖6爲本發明實施例透射電鏡微栅中另一種石墨烯片-奈 米碳管膜結構的結構示意圖。 ....... ........ ： " ：. 圖7爲本發明實施例透射電鏡微栅中一種石墨烯片-奈米 碳管骐結構的透射電鏡照片、 圖8爲本發明實施例表面具有樣品的透射電鏡微栅的結構 示意圖。 圖9爲應用本發明實施例透射電鏡微栅觀察奈米金顆粒的 透射電鏡照片。 圖10爲圖9中應用本發明實:¾參|透#電鏡微栅觀察奈米金 顆粒的高分辨率透射電鏡照片。 【主要元件符號說明】 透射電鏡微栅 100 通孔 112 ------- 金屬網格 110 - _-^一— 石墨烯片-奈米碳管膜複合、结 120 構 一_一__ -----------------^ 奈米碳管膜結構 122 表單編號A0101 第18頁/共33頁 0982044562-0 098126005 石墨婦片 124 微孔 126 奈米碳管線 128 樣品 200 201103862 Ο 098126005 表單編號Α0101 第19頁/共33頁 0982044562-02 is a scanning of a carbon nanotube film in a TEM microgrid according to an embodiment of the present invention. 098126005 Form No. Α0101 No. 17 / Total 33 Page 0982044562-0 201103862 Electron micrograph. [0070] FIG. 3 is a view showing a multilayered carbon nanofilm formed by a plurality of layers in a transmission electron microscope micro-gate according to an embodiment of the present invention. [0070] FIG. Scanning electron micrograph of the structure of the carbon nanotube membrane. 4 is a schematic structural view of a transmission electron microscope micro-gate according to an embodiment of the present invention. Fig. 5 is a structural schematic view showing a structure of a graphene sheet-nanocarbon tube in a transmission electron microscope micro-gate according to an embodiment of the present invention. Fig. 6 is a structural schematic view showing another structure of a graphene sheet-carbon nanotube film in a transmission electron microscope micro-gate according to an embodiment of the present invention. . . .......: ": Figure 7 is a transmission electron micrograph of a graphene sheet-nanocarbon tube structure in a transmission electron microstrip micro-gate according to an embodiment of the present invention, Fig. 8 It is a schematic structural view of a TEM micro-gate having a sample on the surface of the embodiment of the present invention. Fig. 9 is a transmission electron micrograph of a nano-particle observed by a transmission electron microstrip micro-gate according to an embodiment of the present invention. Fig. 10 is a high-resolution transmission electron micrograph of the nano gold particles observed in Fig. 9 by applying the present invention: 3⁄4 参?透#electron micro-gate. [Main component symbol description] TEM micro-gate 100 through hole 112 ------- Metal mesh 110 - _-^一 - graphene sheet - nano carbon tube film composite, knot 120 structure one____ -----------------^ Nano carbon tube membrane structure 122 Form No. A0101 Page 18 of 33 0982044562-0 098126005 Graphite wafer 124 Microporous 126 Nano carbon pipeline 128 Sample 200 201103862 Ο 098126005 Form No. 1010101 Page 19 of 33 0982044562-0