1362678 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種透射電鏡微栅的製備方法。 【先前技術】 在透射電子顯微鏡中，多孔碳支持膜（微栅）係用 二載粉末樣品’進行透射電子顯微鏡高分辨像 RTEM)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曰 先前技術中，該應用於透射電子顯微鏡的微柵 通吊係在銅網或鎳網等金屬網袼上覆蓋一層多孔有機 膜’再，鍍-層非晶碳臈製成的。然而，在實際應用中， 在觀察尺f小於5奈米的顆粒的透射電鏡高分辨像 :察=:晶射電鏡 十年代初以來，以奈米碳管（請參 見Hellcal mi咖ubules 〇f㈣州如以知，灿―〇1362678 IX. Description of the Invention: [Technical Field] The present invention relates to a method of preparing a transmission electron microstrip. [Prior Art] In a transmission electron microscope, a porous carbon supporting membrane (microgrid) is an important tool for observation of a two-loaded powder sample by high-resolution image transmission electron microscopy (TEM). With the continuous development of nanomaterial research, the application of microgrids in the field of electron microscopy of nanomaterials. In the prior art, the microgates used in transmission electron microscopy are attached to metals such as copper or nickel mesh. The mesh is covered with a layer of porous organic film', and then plated-layered amorphous carbon crucible. However, in practical applications, high-resolution images of TEM in the observation of particles with a ruler f of less than 5 nm: see =: crystal electron microscopy since the beginning of the decade, with carbon nanotubes (see Hellcal mi ubules 〇f (four) states If you know, Can-〇
Iijima，vol 354, P56(199l))爲代表的奈米材料以其獨特的 結構和性们丨起了人們極大的關注。將奈米碳管薄膜應 用於微栅的4作’有利於提高透射電鏡的分辨性能。缺 而’奈米碳管不易分散，並且奈米碳管薄膜的製備過程 複雜’難讀用於A批量製備透射電鏡微栅。 有繁於此，提供—種對於奈米級顆粒，尤其直徑小 於5奈米的顆粒，更客县满思 又谷易獲付效果更好地透射電鏡高分 辨像的透射電鏡微栅的製備方法實為必要。 【發明内容】 7 1362678 -種透射電鏡微栅的製備方法 供多個金屬網格間隔設置在__基 ^括以下步戰：提 .中拉取獲得至少—奈米碳底：面，從奈米碳管陣列 * m u ^ ^ j 、、 B 、，將至少—奈米碳管薄腺 覆盍在該多個間隔設置的金屬網格上 U相 該奈米碳管薄膜和金屬網格；及斷開溶劑處理 的“…膜’從而形成多個透射電鏡微栅。 相較於先前技術，所述的透射電鏡微棚的製備方法， 順排奈米碳管陣列連續抽出奈米碳管薄膜並一 一人復盖在夕個金屬網格上，方法簡單、快捷，通過去除全 2網格以外的奈采碳管薄膜，可批量製備性㈣定的透射 電鏡用微柵。利用奈米碳管的吸附特性，這種微栅有助於 觀察尺寸小於5nm的奈米顆粒的透射電鏡高分辨像。 【實施方式】 下面將結合附圖對本發明作進一步的詳細說明。 請參閱目1及目2A-2D，本發明實施例透射電鏡微棚 的製備方法主要包括以下幾個步驟： 步驟一：提供一基底12及多個用於透射電鏡中的金屬 網格14,將該多個金屬網格14間隔設置於該基底12表面。 δ玄基底12具有一平整表面，其材料不限。本實施例 中，δ玄基底12爲一陶瓷片。該金屬網格14爲一形成有一 個或多個通孔的金屬片。該通孔的直徑爲1〇微米〜2毫米。 a亥金屬網格14材料爲銅或其他金屬材料，該金屬網格14 的網孔孔徑退大於奈米碳管薄膜16中相鄰奈米碳管之間 的距離，或多層奈米碳管薄膜16重叠形成的奈米碳管薄臈 8 1362678 結構的微孔孔徑。 兩個相鄰的金屬網格14之間的距離不能過大或過 小’過大則不利於提高透射電鏡微栅的生産效率，過小則 使後續步驟中對奈米碳管薄膜16的加工難度增加，不利於 降低生產成本。當在後續步驟中使用雷射光束18照射方法 處理奈米碳管薄膜16時，該兩個相鄰的金屬網格14之間The nanomaterials represented by Iijima, vol 354, P56 (199l)) have attracted great attention due to their unique structure and properties. Applying a carbon nanotube film to the micro-gate is advantageous in improving the resolution of the transmission electron microscope. The 'nano carbon tube is not easy to disperse, and the preparation process of the carbon nanotube film is complicated'. It is difficult to read for the preparation of TEM micro-gates in batches. There are many kinds of methods for preparing nanometer-sized particles, especially those having a diameter of less than 5 nanometers, and a method for preparing a transmission electron micro-gate with a high-resolution image of a transmission electron microscope with a better effect. It is really necessary. SUMMARY OF THE INVENTION 7 1362678 - A method for preparing a transmission electron microstrip for a plurality of metal grids is set in the __ base including the following steps: extracting and extracting at least - nanocarbon bottom: surface, from Nai a carbon nanotube array* mu ^ ^ j , , B , , and at least a thin carbon nanotube of a carbon nanotube overlying the plurality of spaced metal grids, U-phase the carbon nanotube film and the metal grid; Dissolving the solvent treated "...film" to form a plurality of transmission electron microstrips. Compared to the prior art, the TEM microcavity is prepared by continuously extracting the carbon nanotube film from the array of aligned carbon nanotubes and One person covers the metal mesh on a single day, the method is simple and fast, and the micro-gate for transmission electron microscopy can be prepared in batches by removing the carbon nanotube film except the full 2 mesh. The adsorption characteristics of the microgrid are useful for observing a TEM high resolution image of nanoparticle having a size of less than 5 nm. [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings. -2D, embodiment of the present invention, transmission electron microscopy micro-shed The preparation method mainly includes the following steps: Step 1: providing a substrate 12 and a plurality of metal meshes 14 for use in a transmission electron microscope, and spacing the plurality of metal meshes 14 on the surface of the substrate 12. There is a flat surface, and the material thereof is not limited. In this embodiment, the δ mysterious substrate 12 is a ceramic piece. The metal mesh 14 is a metal piece formed with one or more through holes. The diameter of the through hole is 1 〇 microns ~ 2 mm. The material of the metal grid 14 is copper or other metal material, and the mesh aperture of the metal grid 14 is larger than the distance between adjacent carbon nanotubes in the carbon nanotube film 16, or The microporous aperture of the carbon nanotube thin film formed by the multi-layered carbon nanotube film 16 is overlapped. The distance between two adjacent metal meshes 14 cannot be too large or too small, which is not conducive to the improvement of transmission electron microscopy. The production efficiency of the grid is too small to increase the processing difficulty of the carbon nanotube film 16 in the subsequent step, which is disadvantageous for reducing the production cost. When the carbon nanotube film 16 is treated by the laser beam 18 irradiation method in the subsequent step, The two adjacent Between metal grids 14
的距離應大於雷射光束18照射在奈米碳管薄膜16表面I 所形成光斑的直徑，本實施例優選爲5〇〜2〇〇微米。優選 地，爲提高奈米碳管薄膜16的利用率並方便切割，可將該 多個金屬網格14緊密並規則排列於該基底12表面。本實 施例中’該多個金屬網格14沿行及列排列於該基底12 ^ 面。 步驟 提供 奈米碳管陣列，優選地，該陣列爲超 順排奈米碳管陣列。 ^本κ她例中，超順排奈米碳管陣列的製備方法採用化 學氣相沈積法，並且辦半顿5 a ^ / 、， "具體步驟包括：（a)提供一平整基底， “土底可达用P型或心矽基底，或選用形成有氧化層的 石夕基底’本實施例優選純用4英寸㈣基底；⑴在基 " 句勻形成一催化劑層，該催化劑層材料可選用鐵 (Fe)、# (Cg)、鎳（Ni)或其任意組合的合金之—⑴ 字述少成有催化劑層的基底在700〜900°C的空氣中退火 約30分鐘〜9〇分鐘.Γ# ^ , ^ ^ A (d)將處理過的基底置於反應爐中’ c ^ 加熱到500〜740〇C，然後通入碳源氣體 反應約5〜3 〇分妒·. 、$ ’生長得到超順排奈米碳管陣列，其高 9 1362678 又爲〇 400微米。§亥超順排奈米碳管陣列爲多個彼此平 .灯且垂直於基底生長的奈米碳管形成的純奈米碳管陣列。 過上^控制生長條件’該超順排奈米碳管陣列中基本不 3有雜貝，如無定型碳或殘留的催化劑金屬顆粒等。該奈 米石反官P車列中的奈米碳管彼此通過凡德瓦爾力緊密接觸形 成陣列。 尸本實施例中碳源氣可選用乙块等化學性質較活潑的碳 鲁風化合物’保護氣體可選用氮氣、氨氣或惰性氣體。 步驟二.從上述奈米碳管陣列中抽取獲得至少一具有 一疋寬度和長度的奈米碳管薄膜16。 + 採用一拉伸工具從奈米碳管陣列中拉取獲得奈米碳管 4膜16。其具體包括以下步驟：（a)從上述奈米碳管陣列 中選定-定寬度的多個奈米碳管片斷，本實施例優選爲採 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 的多個奈米石炭管片_;(b) α 一定速度沿基本垂直於奈米 _碳管陣列生長方向拉伸該多個奈米碳管片斷，以形成一奈 米碳管薄膜16 » 在上述拉伸過程中，該多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，該選定的多個奈米碳管片斷分別與其他奈米碳管片斷 I尾相連地連續地被拉出，從而形成一奈米碳管薄膜16。 亥不米石厌管薄膜16爲定向排列的多個奈米碳管束首尾相 連升/成的具有一疋寬度的奈米破管薄膜16。該奈米碳管薄 膜16中奈米碳管的排列方向基本平行於奈米碳管薄膜16 的拉伸方向。 本知例—’遠奈米碳管薄膜1 列所生長的基底的尺寸有關， ^;度與奈Μ官陣 限，可根據實際需求制得。本;;薄膜16的長度不 生長r排奈米碳管陣列，該二管 ::::米奈米—相鄰奈米碳管之間的距: 步驟四.將上⑽得的奈米碳管薄膜16覆蓋在上述多 個間隔設置的金屬網格14上。 瓜 該奈米碳管薄膜16的面積應足够大，從而可 : 石厌官薄膜16完全覆蓋該多個間隔設置的金屬網 格14。 可以理解’可進—步將多個奈米碳管薄膜^依次重叠 地鋪設在多個金屬網格14上。具體地’可將抽取獲得的一 奈米碳管薄膜16直接覆蓋在金屬網格14上，再將另一或 ^多的奈米碳管_ 16沿職角度依次覆蓋上—奈米碳 管薄膜16，從而形成一覆蓋於多個金屬網格14上的奈米 碳管薄膜結構。該多個奈米碳管薄膜16的鋪設角度不限， 爲0。< α $ 90。，本實施例優選爲9〇。。 由於本貫施例步驟一中提供的超順排奈米碳管陣列中 的奈米碳管非常純淨，且由於奈米碳管本身的比表面積非 吊大’故5玄奈米碳管薄膜16本身具有較强的枯性。多層奈 米碳管薄膜16之間由於凡德瓦爾力緊密連接形成一穩定 的奈米碳管薄膜結構。該預定的角度可根據需求設定爲相 11 1362678 同的角度或不同的角度。該奈米碳管薄膜 薄膜16的層數不限。 甲不水石反& 另，也可將多層抽取獲得的奈米碳管薄膜16以預定的 角度層層堆叠鋪設於—框架結構上，從而預先形成— =薄膜結構’再將該奈米碳管薄膜結構覆蓋在金屬： 本實施例還可利用將多層奈米碳管薄膜16部分堆或 形成具有任意寬度和長度的奈米碳管薄膜結構，不: ，例上述方法從奈米碳管陣列直接拉出的奈米碳： 还的寬度限制。 寻膜 步驟五··使用有機溶劑處理上述奈米碳管薄獏玉 而使該奈米碳管薄膜16和金屬網格14結合緊宓。、心 上述有機溶劑爲揮發性有機溶劑，如乙醇:甲醇 =古二氣乙H氯仿，本實施财採用乙醇。該有機溶劑 Ιί接滴在奈米破管薄膜16上，使該奈米碳管薄膜16和 、，屬網格14結合緊密。另，可將上述覆蓋有奈米碳管薄膜 16的金屬網格14整個浸入盛有有機溶劑的容器中浸潤。、 該奈米碳管薄膜16經有機溶劑浸潤處理後，在揮發性 有機溶劑的表©張力的作用τ，奈米碳管薄膜16中的_ 的奈米碳管片斷會部分聚集成奈求碳管束。該奈米碳管薄 膜16中奈米碳管聚集成束’使得該奈米碳管薄臈中平 行的奈米碳管束之間基本相互間隔。當將多層奈米碳管薄 膜16沿不同方向重叠覆蓋金屬網格14時，多層奈米碳管 賴16中的奈米碳管束交叉排列形成微孔結構。這些微孔 12 丄观678 係由順序排列而又互相交叠的奈米碳管，及奈米碳管束構 成的。 本技術領域技術人員應明白，本實施例奈米碳管薄膜 結構中的微孔結構與奈米碳管薄膜16的層數有關，當層數 越多時，所形成的微孔結構的孔徑越小。如，當層數爲四 層時’微孔的尺寸分佈範圍大約從幾個奈米到丄微米。這 些微孔可支撐奈米顆粒，奈米線，奈米棒等，以用來進行 透射電鏡觀察分析。 步驟六：待有機溶劑揮發後，斷開該多個金屬網格u 之間的奈米奴官薄膜16，從而形成多個透射電鏡微棚。 具體地’可採用雷射光束18聚焦照射去除覆蓋於金屬 網格^以外的奈米碳管薄膜16，其具體包括以下步驟： 盲先，提供一雷射光束18。本實施例中，雷射光束18 :通過傳統的氣離子雷射器或二氧化碳雷射器産生，其功 率爲5〜30瓦（W)，優選爲18w。The distance should be larger than the diameter of the spot formed by the laser beam 18 on the surface I of the carbon nanotube film 16, which is preferably 5 〇 2 2 μm. Preferably, in order to improve the utilization of the carbon nanotube film 16 and facilitate cutting, the plurality of metal meshes 14 may be closely and regularly arranged on the surface of the substrate 12. In the present embodiment, the plurality of metal meshes 14 are arranged in rows and columns on the surface of the substrate. The step provides a carbon nanotube array, preferably the array is a super-sequential carbon nanotube array. In the case of κ, in her case, the preparation method of the super-sequential carbon nanotube array is carried out by chemical vapor deposition, and the process is half a 5 a ^ / , " specific steps include: (a) providing a flat substrate, " The soil bottom can be made of a P-type or a sputum base, or a stone-like base formed with an oxide layer. This embodiment preferably uses a 4 inch (four) substrate purely; (1) a catalyst layer is formed in the base, and the catalyst layer material is formed. An alloy of iron (Fe), #(Cg), nickel (Ni) or any combination thereof may be selected - (1) The substrate having less catalyst layer is annealed in air at 700 to 900 ° C for about 30 minutes to 9 〇 Minutes.Γ# ^ , ^ ^ A (d) Place the treated substrate in a reaction furnace 'c ^ Heat to 500~740 °C, then pass the carbon source gas to react about 5~3 〇. $ 'growth to obtain a super-sequential carbon nanotube array with a height of 9 1362678 and a size of 〇400 μm. § Hai Chao Shun Nike carbon nanotube array is a plurality of carbon nanotubes that are flat with each other and grow perpendicular to the substrate. The formation of a pure carbon nanotube array. Over the control of growth conditions 'the super-sequential carbon nanotube array is basically no 3 miscellaneous, such as amorphous Carbon or residual catalyst metal particles, etc. The carbon nanotubes in the nanometer anti-P train are in close contact with each other to form an array by van der Waals force. In the corpse embodiment, the carbon source gas may be chemically selected such as a block. The more active carbon-lubricating compound 'protective gas can be selected from nitrogen, ammonia or inert gas. Step 2. Extract at least one carbon nanotube film 16 having a width and length from the above carbon nanotube array. A stretching tool is taken from the carbon nanotube array to obtain a carbon nanotube 4 film 16. The concrete step comprises the following steps: (a) selecting a plurality of carbon nanotubes of a predetermined width from the carbon nanotube array. Fragment, this embodiment preferably uses a tape having a certain width to contact the carbon nanotube array to select a plurality of nano-carboniferous tube sheets of a certain width _; (b) α a certain speed along a substantially perpendicular to the nano-carbon tube array growth Stretching the plurality of carbon nanotube segments in a direction to form a carbon nanotube film 16 » During the stretching process, the plurality of carbon nanotube segments are gradually separated from the substrate in the stretching direction under tensile force Due to Van der In the action of force, the selected plurality of carbon nanotube segments are continuously pulled out in conjunction with the other tails of the other carbon nanotubes to form a carbon nanotube film 16. The hexamethine film 16 The nano tube-breaking film 16 having a width of one turn is connected to the aligned carbon nanotube bundles. The arrangement of the carbon nanotubes in the carbon nanotube film 16 is substantially parallel to the carbon nanotube film. The direction of stretching of 16 . This example - 'the size of the base of the nanometer carbon tube film grown in the column, ^; degree and the limit of the natrix can be obtained according to actual needs. Ben; The length of the r-row carbon nanotube array is not grown, the distance between the two tubes::::Minet-adjacent carbon nanotubes: Step 4. The carbon nanotube film 16 obtained on the above (10) is covered above. A plurality of spaced metal grids 14 are provided. The area of the carbon nanotube film 16 should be sufficiently large so that the stone film 16 completely covers the plurality of spaced metal grids 14. It will be understood that a plurality of carbon nanotube films can be sequentially laid on a plurality of metal grids 14 in an overlapping manner. Specifically, a carbon nanotube film 16 obtained by extraction can be directly covered on the metal mesh 14, and another carbon nanotube 16 can be sequentially covered with a carbon nanotube film. 16, thereby forming a carbon nanotube film structure overlying the plurality of metal grids 14. The laying angle of the plurality of carbon nanotube films 16 is not limited and is zero. < α $ 90. This embodiment is preferably 9 Å. . Since the carbon nanotubes in the super-sequential carbon nanotube array provided in the first step of the present embodiment are very pure, and because the specific surface area of the carbon nanotubes itself is not large, the carbon nanotube film 16 It has a strong dryness. The multi-layered carbon nanotube film 16 is closely connected by van der Waals force to form a stable carbon nanotube film structure. The predetermined angle can be set to the same angle or different angles of the phase 11 1362678 according to requirements. The number of layers of the carbon nanotube film 16 is not limited. In addition, the carbon nanotube film 16 obtained by multi-layer extraction may be stacked on the frame structure at a predetermined angle to form a pre-formed film structure and then the carbon nanotube. The film structure is covered by the metal: This embodiment can also utilize the partial stacking or forming of the multi-layered carbon nanotube film 16 to form a carbon nanotube film structure having any width and length, and the method described above is directly from the carbon nanotube array. Pull out the nano carbon: also the width limit. Film-forming Step 5: The above-mentioned carbon nanotube film 16 is treated with an organic solvent to bond the carbon nanotube film 16 and the metal mesh 14 to each other. The above organic solvent is a volatile organic solvent, such as ethanol: methanol = ancient two gas, H chloroform, and ethanol is used in this implementation. The organic solvent 接ί is dropped on the nano tube-breaking film 16, so that the carbon nanotube film 16 and the genus mesh 14 are tightly bonded. Alternatively, the metal mesh 14 covered with the carbon nanotube film 16 described above may be entirely immersed in a container containing an organic solvent to be infiltrated. After the carbon nanotube film 16 is treated by the organic solvent infiltration, the surface of the volatile organic solvent is subjected to the tension τ, and the carbon nanotube fragments of the carbon nanotube film 16 are partially aggregated into the carbon. Tube bundle. The carbon nanotubes in the carbon nanotube membrane 16 are gathered into a bundle so that the parallel carbon nanotube bundles in the nanotubes are substantially spaced apart from each other. When the multilayered carbon nanotube film 16 is overlaid to cover the metal mesh 14 in different directions, the carbon nanotube bundles in the multilayered carbon nanotubes 16 are arranged in a crosswise manner to form a microporous structure. These micropores 12 678 678 are composed of carbon nanotubes arranged in series and overlapping each other, and a bundle of carbon nanotubes. It will be understood by those skilled in the art that the microporous structure in the structure of the carbon nanotube film of the present embodiment is related to the number of layers of the carbon nanotube film 16. When the number of layers is larger, the pore diameter of the formed microporous structure is higher. small. For example, when the number of layers is four layers, the size distribution of the micropores ranges from about several nanometers to about one micron. These micropores can support nanoparticle, nanowires, nanorods, etc., for transmission electron microscopic observation and analysis. Step 6: After the organic solvent is volatilized, the nano slave film 16 between the plurality of metal grids u is broken, thereby forming a plurality of transmission electron microscope micro-sheds. Specifically, the laser beam 18 can be focused and irradiated to remove the carbon nanotube film 16 over the metal grid, which specifically includes the following steps: blindly, a laser beam 18 is provided. In this embodiment, the laser beam 18 is produced by a conventional gas ion laser or carbon dioxide laser having a power of 5 to 30 watts (W), preferably 18 watts.
其次，將該雷射光束18聚焦照射至覆蓋於所述多個金 屬網格Μ以外的奈米碳管薄膜16表面，斷開該多個金屬 14之間的奈米石厌官薄膜16。該雷射光束μ可通過一 透鏡聚焦後從正面直接照射在上述奈米碳管薄膜Μ表 :隹=解’該雷射光束18可採用垂直照射或傾斜照射 碳管薄膜16表面。上述奈米碳管薄膜吸收 使奈米破管薄膜16斷開中的氧發生反應並分解’從而 可以理解’可採用以下方法斷開多個金屬網格14之間 13 1362678 的奈米破管薄骐16。 方法一：移動雷射光束18，沿每一金屬網格14邊沿 照射該奈米碳管薄膜16 —周，形成一沿金屬網格14邊沿 s環繞金屬網格14的分離區域144,從而使覆蓋於金屬網格 14上的奈米碳管薄膜16與覆蓋於金屬網格14以外的奈米 碳管薄膜16分離。 方法二：移動雷射光束18，照射全部金屬網格14以 外的奈米碳管薄膜16，從而去除全部金屬網格14以外的 _奈米碳管薄膜16。 方法三：當該金屬網格14爲按陣列方式排列於基底 12表面時，移動雷射光束18，沿直線照射金屬網格14行 間及列間空隙’從而使多個金屬網格14之間的奈米碳管薄 膜16斷開。 ‘ 上述斷開多個金屬網格之間的奈米碳管薄膜16步 驟中，該雷射光束18移動及照射的線路可通過電腦程序控 •制。 可以理解，也可採用先前技術中的其它方法去除覆蓋 於金屬網格14以外的奈米碳管薄膜16。如在該奈米碳管 薄膜16表面塗覆光刻膠’利用化學或物理刻蝕的方法去除 金屬網格14以外的奈米碳管薄膜16。 請參閱圖3及圖4，本實施例依照上述方法製備得到 的透射電鏡微栅結構10，其包括一金屬網格14及覆蓋在 金屬網格14表面的奈米碳管薄膜結構。該金屬網格“爲 一形成有一個或多個通孔142的金屬片。該通孔142的直 Ϊ362678 從A 10微米〜2毫米。該金屬網格14材料爲銅或其他金屬 =料’该金屬網格14通孔142的孔徑遠大於奈米碳管薄膜 2構的微孔孔徑。該奈米碳管薄膜結構包括一層奈米碳管 溥膜16,或者也可爲多層奈米碳管薄臈16按照預定的角 ，，叠形成的微孔薄膜結構。該微孔薄膜的孔徑與奈米碳 官薄臈16的層數有關’可爲丄奈米〜1〇微米。Next, the laser beam 18 is focused and irradiated onto the surface of the carbon nanotube film 16 covering the plurality of metal grids, and the nano-stone barrier film 16 between the plurality of metals 14 is broken. The laser beam μ is focused by a lens and directly irradiated from the front surface to the surface of the carbon nanotube film: 隹 = solution The laser beam 18 can be irradiated with a vertical or oblique illumination on the surface of the carbon tube film 16. The above-mentioned carbon nanotube film absorption reacts and decomposes the oxygen in the breaking of the nano tube film 16 to understand that the following method can be used to break the micro-tube thinning between the plurality of metal meshes 14 13 1362678骐16. Method 1: Moving the laser beam 18, illuminating the carbon nanotube film 16 along the edge of each metal mesh 14 to form a separation region 144 surrounding the metal mesh 14 along the edge s of the metal mesh 14 so as to cover The carbon nanotube film 16 on the metal mesh 14 is separated from the carbon nanotube film 16 which is covered outside the metal mesh 14. Method 2: The laser beam 18 is moved to illuminate the carbon nanotube film 16 outside the entire metal mesh 14, thereby removing the carbon nanotube film 16 other than the entire metal mesh 14. Method 3: When the metal grid 14 is arranged in an array on the surface of the substrate 12, the laser beam 18 is moved, and the metal grid 14 is irradiated along the line and the inter-column gap ', thereby making the metal grid 14 The carbon nanotube film 16 is broken. ‘In the above-described step of disconnecting the carbon nanotube film 16 between the plurality of metal grids, the line in which the laser beam 18 is moved and illuminated can be controlled by a computer program. It will be appreciated that the carbon nanotube film 16 overlying the metal mesh 14 may also be removed by other methods in the prior art. The surface of the carbon nanotube film 16 is coated with a photoresist. The carbon nanotube film 16 other than the metal mesh 14 is removed by chemical or physical etching. Referring to FIG. 3 and FIG. 4, the TEM micro-gate structure 10 prepared according to the above method comprises a metal mesh 14 and a carbon nanotube film structure covering the surface of the metal mesh 14. The metal mesh "is a metal piece formed with one or more through holes 142. The through hole 142 has a straight Ϊ 362678 from A 10 μm to 2 mm. The metal mesh 14 material is copper or other metal = material ' The aperture of the metal mesh 14 through hole 142 is much larger than the micropore diameter of the carbon nanotube film 2. The carbon nanotube film structure includes a layer of carbon nanotube film 16, or may be a thin layer of carbon nanotubes.臈16 is a microporous film structure formed by stacking at a predetermined angle. The pore diameter of the microporous film is related to the number of layers of the nanometer carbon thin crucible 16 'may be 丄 nanometer ~ 1 〇 micron.
請參閱® 5,冑本發明實施例透射電鏡微棚結構忉中 =用四層奈米碳管薄膜16構成的奈米碳管薄膜結構的掃 4電鏡照片。該四層奈米碳管薄膜16以9〇〇角重叠形成微 孔薄膜結構，每—層奈米碳管薄膜16中的奈米碳管均定向 排列’兩奈米碳管薄膜16之間通過凡德瓦爾力結合“亥太 =薄膜16中的奈米碳管聚集成束，該奈米碳管薄膜： 構中不米碳管束交又形成多個微孔結構，其中微孔直 1奈米〜10微米。 本實施例透射電鏡微栅10在應用時， =微孔支持具有較大尺寸的奈米顆粒，奈米線r;:: ，來進行透射電鏡觀察分析。對於尺寸小於5nm的單 =米顆粒來說，微孔的仙η，起作㈣主要係奈 :反管的吸附作用，這些尺寸極小的奈米顆粒能够被轉定 和=附在奈米碳管管壁邊沿，便於進行觀察。請參閱圖6 θ 7’圖中黑色顆粒爲待觀察的奈米金顆粒。該 ==吸附在奈米碳管管壁邊沿，有利於觀察奈；金 顆粒的尚分辨像。 另’由於用於抽取奈米碳管薄膜16的超順排奈米碳管 15 1362678 陣列中的碳管純淨度高，尺寸均_，管壁缺陷少。本實施 ，例透射電鏡微柵1〇對承載於其上的待觀測樣品的形貌和 •結構分析等干擾小，對吸附於其上的奈米顆粒的高分辨像 影響很小。 本發明實施例所提供的透射電鏡微栅的製備方法，苴 通過從超順排奈米碳管陣列可連續抽出奈米碳管薄膜並二 次覆蓋在多個金屬網格上，方法簡單、快捷，通過去除金 屬網格以外的奈米碳管薄膜，可批量製備性質穩定的透射 電鏡用微栅。同時，利用奈米碳管的吸附特性，有助於觀 察尺寸小於5nm的奈米顆粒的透射電鏡高分辨像。 ^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巾請專利範圍。舉凡f知本案技藝 =人士k依本發明之精神所作之等效修飾或變化，皆應涵 蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1爲本技術方案實施例透射電鏡微柵的製備方法的 流程示意圖。 一圖2A-2D為本技術方案實施例透射電鏡微栅的製備工 藝流程圖。 圖3爲本技術方案實施例透射電鏡微栅的結構示魚 圖。 、 圖4爲本技術方案實施例透射電鏡微栅的掃描電鏡 (SEM)照片。 16 圖5爲本技術方案實施例透射 膜的透射電鏡照片。 包鏡微栅中奈米碳管薄 圖6爲應用本技術方案實施例透射電鏡微栅觀察奈来 金顆粒的透射電鏡照片。 圖7爲圖6的局部放大示意圖。 【主要元件符號說明】 透射電鏡微栅結構 基底 鲁金屬網格 10 12 14 通孔 142 分離區域 144 奈米碳管薄膜 丄b 雷射光束 μPlease refer to ® 5, in the embodiment of the present invention, a transmission electron microscope micro-shed structure, a photomicrograph of a carbon nanotube film structure composed of a four-layered carbon nanotube film 16. The four-layered carbon nanotube film 16 is overlapped at a 9-inch angle to form a microporous film structure, and the carbon nanotubes in each of the layers of the carbon nanotube film 16 are aligned to pass between the two carbon nanotube films 16 Van der Valli combines "Hai Tai = the carbon nanotubes in the film 16 to form a bundle, the carbon nanotube film: the structure of the carbon nanotube bundles and the formation of a plurality of microporous structures, wherein the micropores straight 1 nm ~10 μm. In this embodiment, the TEM micro-grid 10 is used when the micro-hole supports nano-particles with a larger size, and the nanowire r;:: is used for observation by transmission electron microscopy. For a single size less than 5 nm = rice particles, the pores of the η, starting from (4) the main line of Nai: the adsorption of the back tube, these small size nanoparticles can be transferred and = attached to the edge of the carbon nanotube wall, easy to carry out See Figure 6. The black particles in the θ 7' diagram are the nano gold particles to be observed. The == adsorption on the edge of the carbon nanotube wall is beneficial to observe the Nai; the resolving image of the gold particles. Carbon tube pure in the array of super-shoring carbon nanotubes 15 1362678 for extracting carbon nanotube film 16 The netness is high, the size is _, and the tube wall defect is small. In this embodiment, the transmission electron microscopy micro-gate 1〇 has little interference to the morphology and structural analysis of the sample to be observed carried thereon, and the nano-adsorbed thereon. The high-resolution image of the rice particles has little effect. The preparation method of the TEM micro-grid provided by the embodiment of the invention can continuously extract the carbon nanotube film from the super-aligned carbon nanotube array and cover the film twice. On a metal grid, the method is simple and fast. By removing the carbon nanotube film outside the metal grid, the microgrid for the stable transmission electron microscope can be prepared in batches. At the same time, the adsorption characteristics of the carbon nanotubes are helpful. Observing the high-resolution image of the TEM of the nano-particles having a size of less than 5 nm. 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 is only the preferred embodiment of the present invention. For example, it is not possible to limit the scope of the patent application in this case. Any equivalent modifications or changes made by the person in accordance with the spirit of the present invention should be included in the scope of the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic flow chart of a preparation method of a transmission electron microstrip micro-gate according to an embodiment of the present technology. FIG. 2A-2D is a flow chart of a preparation process of a transmission electron microscope micro-gate according to an embodiment of the present technical solution. The structure of the TEM micro-gate is shown in Fig. 4. Fig. 4 is a scanning electron microscope (SEM) photograph of the transmission electron microstrip of the embodiment of the present invention. Fig. 5 is a transmission electron micrograph of the transmission film of the embodiment of the present invention. FIG. 6 is a transmission electron micrograph of the Neyle gold particles observed by the transmission electron microstrip micro-gate in the embodiment of the present invention. FIG. 7 is a partially enlarged schematic view of FIG. 6. [Main component symbol description] Transmission electron microscope Micro-gate structure base Lu metal grid 10 12 14 through hole 142 separation area 144 carbon nanotube film 丄b laser beam μ
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