201137919 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種透射電鏡微柵’尤其涉及一種基於奈米 碳管的透射電鏡微柵。 [0002] 【先前技術】 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，微柵在 〇 [0003] 奈米材料的電子顯微學表徵領域的應用日益廣泛。 先前技術中，該應用於透射電子顯微鏡的微栅通常係在 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’當採用前述微柵對被測樣品 的透射電鏡高分辨像進行成份分析時，被測樣品設置於 非晶碳膜表面，位於被測樣品下方的金屬網格因其經常 含有較多雜質，如金屬氧化物等，對被測樣品成份分析 的干擾較大。 : 〇 [0004] 自九十年代初以來，以奈米碳管（請參見Helical mi-crotubules of graphitic carbon, Nature, Sum-io Iijima，vol 354，p56(1991))為代表的奈米材料 以其獨特的結構和性質引起了人們極大的關注。將奈米 碳管應用於微柵的製作，有利於降低金屬網格對被測樣 品成份分析的干擾。 [0005] 【發明内容】 有鑒於此，提供一種基於奈米碳管的透射電鏡微栅實為 必要，該透射電鏡微柵對被測樣品成份分析的干擾較小 099112609 表單編號A0101 第3頁/共33頁 0992022302-0 201137919 [0006] —種透射電鏡微栅及其製備方法，其中，該透射電鏡微 栅包括一支撐環及一片狀奈米碳管結構，該片狀奈米碳 管結構的週邊通過前述支撐環固定，該片狀奈米碳管結 構為一多孔結構。 [0007] 相較於先前技術，本發明提供的透射電鏡微柵包括一支 撐環及一片狀奈米碳管結構，片狀奈米碳管結構週邊通 過前述支撐環固定，無需金屬網格，且片狀奈米碳管結 構為純奈米碳管結構，可有效消除傳統微栅中的位於被 測樣品下方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 〇 【實施方式】 [0008] 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。 [0009] 請參閱圖1，本發明實施例提供一種透射電鏡微栅1(^該 透射電鏡微柵10包括一支撐瓖102及一片狀奈米碳管結構 1〇4。前述片狀奈米碳管結構104可為圓片狀，直徑約為3 毫米。前述片狀奈米碳管結構104的週邊通過前述支樓環 102固定。 [0010] 前述支撐環102用於固定前述片狀奈米碳管結構1〇4。前 述支撐環102為圓形的環狀結構。前述支揮環1〇2的直炉 與前述片狀奈米碳管結構104的直徑基本相同，約為3毫 米。前述支撐環102圍成一通孔（圖未標），位於該通孔 099112609 表單編號A0101 第4頁/共33頁 0992022302-0 201137919 Ο 0 處的片狀奈米碳管結構104懸空設置。前述支撐環102的 材料可為金屬或陶究等。前述金屬包括銅、19或錄等。 前述支撐環102的截面（垂直於前述支撐環102所在的平 面的截面）可為方形、圓形、半圓形或梯形等形狀。優 選地，前述支撐環102具有一平整表面，該平整表面用於 與片狀奈米碳管結構104貼合，此時，前述片狀奈米碳管 結構104與支撐環102的平整表面為面接觸，從而可更好 地固定片狀奈米碳管結構104於前述支撐環102。前述片 狀奈米碳管結構104可通過黏結劑、凡德瓦爾力、機械方 式或前述方式的任意結合固定於前述支撐環102。當採用 黏結劑方式固定時，前述支撐環102的表面可預先塗覆一 層黏結劑，然後鋪設片狀奈米碳管結構104於支撐環102 設置有黏結劑的表面，實現固定。當採用凡德瓦爾力方 式固定時，前述片狀奈米碳管結構104可通過自身的黏性 或通過有機溶劑處理直接鋪設於前述支撐環102的表面。 當採用有機溶劑處理方式固定時，前述有機溶劑優選為 揮發性有機溶劑5此時*可將揮發性有機溶劑滴落於铺 設有片狀奈米碳管結構104的支撐環102表面，在揮發性 有機溶劑的作用下，片狀奈米碳管結構104通過凡德瓦爾 力更緊密地貼合固定於前述支撐環102的表面，實現固定 。可以理解，前述片狀奈米碳管結構104與前述支撐環 102之間的固定並不限於前述方式。 [0011] 本實施例中，前述片狀奈米碳管結構104通過機械方式固 定於前述支撐環102。前述支撐環102為直徑3毫米的銅環 。前述支撐環102可包括一圓環狀的支撐環本體102a和四 099112609 表單編號A0101 第5頁/共33頁 0992022302-0 201137919 個延伸部102b。前述片狀奈米碳管結構1〇4固定於4 撐環本體102a和四個延伸部i〇2b之間。4、+、+ '支 月’J迷支撐環本201137919 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a TEM micro-gate, particularly to a TEM micro-gate based on a carbon nanotube. [Prior Art] In a transmission electron microscope, a porous carbon support membrane (microgrid) is an important tool for carrying a powder sample and performing high-resolution image observation (HRTEM) observation by a transmission electron microscope. With the continuous development of nanomaterial research, microgrids are increasingly used in the field of electron microscopy of 〇 [0003] nanomaterials. In the prior art, the microgrid applied to a transmission electron microscope is usually formed by coating a porous organic film on a metal mesh such as a copper mesh or a nickel mesh, and then vapor-depositing an amorphous carbon film. However, when the TEM is used to analyze the composition of the sample to be measured by the micro-gate, the sample to be tested is placed on the surface of the amorphous carbon film, and the metal mesh below the sample to be tested often contains more impurities. Such as metal oxides, etc., the interference of the analysis of the components of the sample to be tested is large. : 〇[0004] Since the early 1990s, nanomaterials represented by carbon nanotubes (see Helical mi-crotubules of graphitic carbon, Nature, Sum-io Iijima, vol 354, p56 (1991)) 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 In view of the above, it is necessary to provide a TEM micro-grid based on a carbon nanotube, which has less interference on the composition analysis of the sample to be tested. 099112609 Form No. A0101 Page 3 / A total of 33 pages 0992022302-0 201137919 [0006] A TEM microgrid and a preparation method thereof, wherein the TEM microgrid comprises a support ring and a sheet of carbon nanotube structure, the sheet carbon nanotube structure The periphery is fixed by the aforementioned support ring, and the sheet-shaped carbon nanotube structure is a porous structure. [0007] Compared with the prior art, the TEM microgrid provided by the present invention comprises a support ring and a sheet of carbon nanotube structure, and the periphery of the sheet-shaped carbon nanotube structure is fixed by the aforementioned support ring without a metal mesh. The sheet-shaped carbon nanotube structure is a pure carbon nanotube structure, which can effectively eliminate the interference of the metal grid located under the sample under test in the traditional micro-grid to analyze the composition of the sample to be tested, thereby facilitating the improvement of the transmission electron microscope. Accuracy in Performing Component Analysis 实施 [Embodiment] [0008] The TEM microgrid of the present invention and its preparation method will be further described in detail below with reference to the accompanying drawings. Referring to FIG. 1, an embodiment of the present invention provides a TEM microgrid 1 (the TEM microgrid 10 includes a support 瓖102 and a sheet of carbon nanotube structure 1〇4. The aforementioned sheet-shaped nanometer The carbon tube structure 104 may be in the form of a disk having a diameter of about 3 mm. The periphery of the sheet-like carbon nanotube structure 104 is fixed by the aforementioned branch ring 102. [0010] The support ring 102 is used to fix the aforementioned sheet-shaped nanometer. The carbon tube structure 1〇4. The support ring 102 has a circular annular structure. The straight furnace of the above-mentioned support ring 1〇2 and the sheet-like carbon nanotube structure 104 have substantially the same diameter, about 3 mm. The support ring 102 encloses a through hole (not shown), and is located in the through hole 099112609 Form No. A0101 Page 4 / Total 33 page 0992022302-0 201137919 片 0 The sheet-shaped carbon nanotube structure 104 is suspended. The aforementioned support ring The material of 102 may be metal or ceramics, etc. The foregoing metal includes copper, 19 or recording, etc. The cross section of the aforementioned support ring 102 (a cross section perpendicular to the plane in which the support ring 102 is located) may be square, circular, semicircular. Or a trapezoidal shape, etc. Preferably, the aforementioned support ring 102 has a The entire surface is used for bonding with the sheet-shaped carbon nanotube structure 104. At this time, the sheet-like carbon nanotube structure 104 is in surface contact with the flat surface of the support ring 102, so that the sheet can be better fixed. The carbon nanotube structure 104 is on the aforementioned support ring 102. The sheet-like carbon nanotube structure 104 can be fixed to the support ring 102 by a bonding agent, a van der Waals force, a mechanical means or any combination of the foregoing. When the agent is fixed, the surface of the support ring 102 may be pre-coated with a layer of adhesive, and then the sheet-shaped carbon nanotube structure 104 is laid on the surface of the support ring 102 provided with the adhesive to achieve fixation. When using the van der Waals force method When fixed, the sheet-like carbon nanotube structure 104 can be directly laid on the surface of the support ring 102 by its own viscosity or by an organic solvent treatment. When the organic solvent treatment is used for fixation, the organic solvent is preferably a volatile organic compound. Solvent 5 at this time* can drip the volatile organic solvent on the surface of the support ring 102 on which the sheet-like carbon nanotube structure 104 is laid, under the action of a volatile organic solvent, The carbon nanotube structure 104 is fixed by the van der Waals force to be more closely attached to the surface of the support ring 102. It can be understood that the aforementioned sheet-like carbon nanotube structure 104 is fixed between the support ring 102 and In the present embodiment, the sheet-like carbon nanotube structure 104 is mechanically fixed to the support ring 102. The support ring 102 is a copper ring having a diameter of 3 mm. The support ring 102 may include the support ring 102. An annular support ring body 102a and four 099112609 Form No. A0101 Page 5 / Total 33 pages 0992022302-0 201137919 Extensions 102b. The sheet-like carbon nanotube structure 1〇4 is fixed between the 4-butt body 102a and the four extensions i〇2b. 4, +, + 'months' J fans support ring
102a和四個延伸部l〇2b可為一體結構。&、+、 W 別述延伸部1〇 的材料與前述支擇環本體l〇2a的材料可相 或不同。僖 選地，則述延伸部102b的材料為具有較好的彎折性斗货 材料，以可實現前述延伸部l〇2b朝支撐環1〇2圓、把的 環102所在圓環的圓心）的方向的彎折， （支撑 進而固定片狀夺 米碳管結構104於前述支撐環本體102a與延伸部丨、 間。本實施例中的延伸部102b的材料與支撐環本體 的材料相同，均為銅。可以理解，前述延伸部1〇扎的^ 量並不限於四個’以可實現片狀奈米碳管結構iQ4較好地 固定於前述支推環本體1023的表面為準，根據前述延伸 部102b的面積，前述延伸部1021)的數量可為—個或複數 [0012] 請一併參見圖2及圖3，前述延伸部i〇2b從支撐環本體 102a向外延伸，其延伸方向為沿延伸處與支撐環本體 102a所在圓環的圓心的連線方向即半徑方向。前述支撐 環本體l〇2a可具有一平整表面i〇2c，前述延伸部1〇2b從 支撐環本體l〇2a的平整表面i〇2c沿半徑方向向外延伸。 優選地’前述延伸部l〇2b與前述支撐環本體l〇2a位於同 —平面内（參見圖2)，或前述延伸部i〇2b所在的平面低 於則述支撐環本體l〇2a所在的平面（圖未示）。前述延 伸部102b的厚度可小於或等於前述支撐環本體1〇23的厚 度。優選地’前述延伸部1〇213的厚度小於前述支撐環本 體l02a的厚度。採用延伸部102b固定片狀奈米碳管結構 099112609 表*單編號A0101 第6頁/共33頁 0992022302-0 201137919 104時，可先將一片狀奈米碳管結構預製體直接鋪設於前 述支撐環本體102a的平整表面102c，然後按支撐環的形 狀即支撐環本體102a外週沿切割前述片狀奈米碳管結構 預製體，形成片狀奈米碳管結構104，最後朝支撐環102 圓心的方向彎折前述延伸部102b，使其覆蓋位於支撐環 本體102a平整表面102c的片狀奈米碳管結構104，從而 實現片狀奈米碳管結構104固定於前述支撐環本體102a與 延伸部102b之間。 ^ [0013] ❹ 前述片狀奈米碳管結構1 04用於支撐被測樣品用於透射電 鏡觀測。前述片狀奈米碳¥結構104為一多孔結構，其具 有複數微孔106。前述微孔106可為通孔，即其可從片狀 奈米碳管結構1 04的一個表面延伸至與該表面相對的另一 表面。前述微孔106的形狀不限，可為圓形、方形、橢圓 形等。前述微孔106的尺寸不限，可根據實際應用需求調 整。前述微孔106的排列方式不限。前述微孔106之間的 距離可相等或不等。優選地，前述微孔106均勻分佈於前 〇 述片狀奈米碳管結構104表面或前述複數微孔106以陣列 形式分佈於前述片狀奈米碳管結構104表面，且相鄰的微 孔106之間的距離相等。相鄰的微孔106之間的距離可大 於1微米。前述微孔106的尺寸約為1微米~200微米。前 述片狀奈米碳管結構104為自支撐結構，且具有一定的支 撐性能。前述自支撐為片狀奈米碳管結構104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一體上 懸空而保持自身片狀結構。前述片狀奈米碳管結構104為 純奈米碳管結構。前述片狀奈米碳管結構104可由至少一 099112609 表單編號A0101 第7頁/共33頁 0992022302-0 201137919 奈米碳管線狀結構編織而成或由至少一奈米碳管膜組成 〇 [0014] 當前述片狀奈米碳管結構104包括複數奈米碳管線狀結構 時，前述複數奈米碳管線狀結構可平行、並排、交叉或 纏繞設置。具體地，前述複數奈米碳管線狀結構可採用 先前技術中的編織方法，如平紋編織或斜紋編織法來製 備前述片狀奈米碳管結構104。前述奈米碳管線狀結構可 由至少一奈米碳管線組成。前述奈米碳管線狀結構為複 數奈米碳管線平行設置組成的一束狀結構或複數奈米碳 管線相互扭轉組成的一絞線結構。前述奈米碳管線由複 數奈米碳管組成，前述奈米碳管線中多數奈米碳管係通 過凡德瓦爾力首尾相連。前述奈米碳管線可為一扭轉的 奈米碳管線或一非扭轉的奈米碳管線。 [0015] 前述非扭轉的奈米碳管線包括複數沿該非扭轉的奈米碳 管線長度方向擇優取向排列的奈米碳管，其掃描電鏡照 片請參見圖4。非扭轉的奈米碳管線可通過將奈米碳管拉 膜通過有機溶劑處理得到。具體地，該奈米碳管拉膜包 括複數奈米碳管片段，該複數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基本相互平 行並通過凡德瓦爾力緊密結合的奈米碳管。該奈米碳管 片段具有任意的長度、厚度、均勻性及形狀。該非扭轉 的奈米碳管線長度不限，直徑為0. 5奈米-1毫米。具體地 ，可將有機溶劑浸潤前述奈米碳管拉膜的整個表面，在 揮發性有機溶劑揮發時產生的表面張力的作用下，奈米 碳管拉膜中的相互平行的複數奈米碳管通過凡德瓦爾力 099112609 表單編號A0101 第8頁/共33頁 0992022302-0 201137919 Ο [0016]The 102a and the four extensions 〇2b may be of a unitary structure. &, +, W The material of the extension 1〇 may be different or different from the material of the aforementioned ring body 102a. Optionally, the material of the extension portion 102b is a material having a good bending material, so that the center of the ring where the extension portion l2b is rounded toward the support ring 1〇2 and the ring 102 is placed) The direction of the bending, (supporting and fixing the sheet-shaped carbon nanotube structure 104 between the support ring body 102a and the extension portion, the material of the extension portion 102b in this embodiment is the same as the material of the support ring body, It is understood that the amount of the above-mentioned extension 1 is not limited to four 'in order to realize that the sheet-like carbon nanotube structure iQ4 is better fixed to the surface of the above-mentioned thrust ring body 1023, according to the foregoing The area of the extending portion 102b, the number of the extending portions 1021) may be one or plural. [0012] Referring to FIG. 2 and FIG. 3 together, the extending portion i2b extends outward from the supporting ring body 102a, and the extending direction thereof It is a radial direction along the line connecting the center of the ring where the support ring body 102a is located, that is, the radial direction. The aforementioned support ring body 10a may have a flat surface i2c which extends radially outward from the flat surface i2c of the support ring body 102a. Preferably, the aforementioned extension portion 102b is located in the same plane as the aforementioned support ring body 102a (see FIG. 2), or the plane of the extension portion i2b is lower than that of the support ring body 10a2a. Plane (not shown). The thickness of the aforementioned extension portion 102b may be less than or equal to the thickness of the aforementioned support ring body 1〇23. Preferably, the thickness of the aforementioned extension portion 1 213 is smaller than the thickness of the aforementioned support ring body 102a. When the extension piece 102b is used to fix the sheet-shaped carbon nanotube structure 099112609 Table * Single No. A0101 Page 6 / Total 33 page 0992022302-0 201137919 104, a piece of carbon nanotube structure preform can be directly laid on the aforementioned support The flat surface 102c of the ring body 102a is then cut into the sheet-like carbon nanotube structure preform in the shape of the support ring, that is, the outer circumference of the support ring body 102a, to form a sheet-like carbon nanotube structure 104, and finally to the center of the support ring 102. The direction of the extension portion 102b is bent to cover the sheet-shaped carbon nanotube structure 104 located on the flat surface 102c of the support ring body 102a, thereby realizing the sheet-shaped carbon nanotube structure 104 to be fixed to the support ring body 102a and the extension portion. Between 102b. ^ [0013] 前述 The aforementioned sheet-like carbon nanotube structure 104 is used to support the sample to be tested for transmission electron microscope observation. The aforementioned sheet-like nanocarbon structure 104 is a porous structure having a plurality of micropores 106. The aforementioned micropores 106 may be through holes, i.e., they may extend from one surface of the sheet-like carbon nanotube structure 104 to the other surface opposite the surface. The shape of the aforementioned micropores 106 is not limited and may be a circle, a square, an ellipse or the like. The size of the aforementioned micropores 106 is not limited and can be adjusted according to actual application requirements. The arrangement of the aforementioned micropores 106 is not limited. The distance between the aforementioned microholes 106 may be equal or unequal. Preferably, the micropores 106 are uniformly distributed on the surface of the sheet-like carbon nanotube structure 104 or the plurality of micropores 106 are distributed in an array on the surface of the sheet-like carbon nanotube structure 104, and adjacent micropores The distance between 106 is equal. The distance between adjacent microholes 106 can be greater than 1 micron. The aforementioned micropores 106 have a size of about 1 micrometer to 200 micrometers. The sheet-like carbon nanotube structure 104 described above is a self-supporting structure and has a certain supporting property. The self-supporting sheet-like carbon nanotube structure 104 does not require a large-area carrier support, but can be suspended in one piece to maintain its own sheet-like structure as long as the supporting force is provided on both sides. The aforementioned sheet-like carbon nanotube structure 104 is a pure carbon nanotube structure. The sheet-like carbon nanotube structure 104 may be woven by at least one 099112609 Form No. A0101 Page 7 / Total 33 page 0992022302-0 201137919 nano carbon line structure or composed of at least one carbon nanotube film [0014] When the aforementioned sheet-like carbon nanotube structure 104 includes a plurality of nanocarbon line-like structures, the aforementioned plurality of nanocarbon line-like structures may be arranged in parallel, side by side, crosswise or wound. Specifically, the foregoing plurality of carbon nanotube-like structures may be prepared by a prior art weaving method such as plain weave or twill weave to form the aforementioned sheet-like carbon nanotube structure 104. The aforementioned nanocarbon line-like structure may be composed of at least one nanocarbon line. The aforementioned nanocarbon line-like structure is a stranded structure in which a plurality of carbon nanotubes are arranged in parallel, or a twisted line structure in which a plurality of nanocarbon lines are twisted with each other. The aforementioned nano carbon pipeline is composed of a plurality of carbon nanotubes, and most of the carbon nanotubes in the above-mentioned nanocarbon pipeline are connected end to end by Van der Waals force. The aforementioned carbon carbon line may be a twisted nano carbon line or a non-twisted nano carbon line. [0015] The aforementioned non-twisted nanocarbon pipeline includes a plurality of carbon nanotubes arranged in a preferred orientation along the length direction of the non-twisted nanocarbon pipeline, and the scanning electron microscope photograph is shown in FIG. 4. The non-twisted nanocarbon line can be obtained by treating the carbon nanotube membrane with an organic solvent. Specifically, the carbon nanotube film comprises a plurality of carbon nanotube segments, and the plurality of carbon nanotube segments are connected end to end by Van der Waals force, and each of the carbon nanotube segments comprises a plurality of substantially parallel to each other and pass through Van der Waals A tightly coupled carbon nanotube. The carbon nanotube segments have any length, thickness, uniformity, and shape. 5纳米毫米毫米。 The non-twisted nano carbon line length is not limited, the diameter is 0.5 nm - 1 mm. Specifically, the organic solvent may be impregnated into the entire surface of the carbon nanotube film, and the parallel carbon nanotubes in the carbon nanotube film may be parallelized by the surface tension generated by the volatilization of the volatile organic solvent. By Van der Valli 099112609 Form No. A0101 Page 8 / Total 33 Page 0992022302-0 201137919 Ο [0016]
[0017] [0018] 099112609 緊密結合，從而使奈米碳管拉膜收縮為一非扭轉的奈米 碳管線。該有機溶劑為揮發性有機溶劑，如乙醇、甲醇 、丙酮、二氣乙烷或氣仿，本實施例中採用乙醇。通過 有機溶劑處理的非扭轉奈米碳管線與未經有機溶劑處理 的奈米碳管膜相比’比表面積減小，黏性降低。前述奈 米破管線及其製備方法請參見范守善等人於2〇〇2年11月 日申請的，於2008年11月21日公告的第1303239號台灣 公告專利’及於2005年12月16日申請，於2009年7月21 日公告的第1312337號台灣公告專利。 前述扭轉的奈米碳管線為採甩一機械力翁前述奈米碳管 拉膜兩端沿相反方向扭轉獲得。該扭轉的奈米碳管線包 括複數繞該扭轉的奈米碳管線軸向螺旋排列的奈米碳管 ’其掃描電鏡照片請參見圖5。進一步地:.，可採用一揮發 性有機溶劑處理該扭轉的奈米碳管線^在揮發性有機溶 劑揮發時產生的表面張力的作用下，處理後的扭轉的奈 米碳管線中相鄰的奈米碳管通過凡德瓦爾力緊密結合， 使扭轉的奈米碳管線的比表面積減小，密度及強度增大 〇 前述奈米碳管臈可為奈米碳管絮化膜、奈米碳管礙壓膜 或奈米碳管拉膜。 前述奈米碳管絮化膜包括複數相互纏繞且均勻分佈的奈 米碳管。前述奈米碳管之間通過凡德瓦爾力相互吸引、 纏繞，形成網路狀結構，以形成一自支撐的奈米碳管絮 化膜’其掃描電鏡照片可參閱圖6。前述奈米碳管絮化膜 各向同性。前述奈米碳管絮化膜可通過對—奈米碳管陣 表單編號Α0101 第9頁/共33頁 201137919 列絮化處理而獲得，具體可參見范守善等人於2007年5月 11日申請，並於2008年11月16日公開的第200844041號 台灣公開專利申請。為節省篇幅，僅引用於此，但前述 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。前述奈米礙管絮化膜並不限於前述製備方法。 前述奈米碳管絮化膜的厚度為1微米至2毫米。前述片狀 奈米碳管結構104可僅包括一層奈米碳管絮化膜，通過調 節其厚度來確保其具有較好的支撐性能。 [0019] 前述奈米碳管碾壓膜包括複數奈米碳管無序排列、沿一 個方向擇優取向排列或沿複數方向擇優取向排列，相鄰 的奈米碳管通過凡德瓦爾力結合。該奈米碳管碾壓膜可 通過採用一平面壓頭沿垂直於前述奈米碳管陣列生長的 基底的方向擠壓前述奈米碳管陣列而獲得，此時前述奈 米碳管碾壓膜中的奈米碳管無序排列，該奈米碳管碾壓 膜各向同性；前述奈米碳管碾壓膜也可採用一滾軸狀壓 頭沿某一固定方向碾壓前述奈米碳管陣列而獲得，此時 前述奈米碳管碾壓膜中的奈米碳管於前述固定方向擇優 取向排列；前述奈米碳管碾壓膜還可採用滾軸狀壓頭沿 不同方向碾壓前述奈米碳管陣列而獲得，此時前述奈米 碳管碾壓膜中的奈米碳管沿不同方向擇優取向排列此時 ，前述奈米碳管碾壓膜可包括複數部分，每個部分中的 奈米碳管沿一個方向擇優取向排列，且相鄰二部分中的 奈米碳管的排列方向可不同。前述奈米碳管碾壓膜的掃 描電鏡照片請參閱圖7。前述奈米碳管碾壓膜的結構及製 備方法請參見范守善等人於2007年6月29曰申請，於 099112609 表單編號A0101 第10頁/共33頁 0992022302-0 201137919 [0020] Ο[0018] 099112609 is tightly bonded to shrink the carbon nanotube film into a non-twisted nanocarbon line. The organic solvent is a volatile organic solvent such as ethanol, methanol, acetone, di-ethane or gas, and ethanol is used in this embodiment. The non-twisted nanocarbon line treated by the organic solvent has a smaller specific surface area and a lower viscosity than the carbon nanotube film which has not been treated with the organic solvent. For the above-mentioned nano-breaking pipeline and its preparation method, please refer to Fan Shou-shan et al., which was filed on November 21, 2002, and announced on November 21, 2008, No. 1303239, Taiwan Announced Patent 'and on December 16, 2005. Application, Taiwan No. 1312337 announced on July 21, 2009, announced the patent. The twisted nanocarbon pipeline is obtained by twisting both ends of the carbon nanotube film in the opposite direction. The twisted nanocarbon line comprises a plurality of carbon nanotubes arranged axially helically around the twisted nanocarbon line. See Figure 5 for a scanning electron micrograph. Further, the volatile nano-carbon pipeline can be treated with a volatile organic solvent to act on the surface tension generated by the volatile organic solvent volatilization, and the adjacent nano-carbon line in the treated twisted carbon nanotube line The carbon nanotubes are tightly combined by van der Waals force to reduce the specific surface area of the twisted nano carbon pipeline, and the density and strength are increased. The carbon nanotubes can be carbon nanotube flocculation membranes or carbon nanotubes. Barrier film or carbon nanotube film. The aforementioned carbon nanotube flocculation membrane comprises a plurality of carbon nanotubes which are intertwined and uniformly distributed. The aforementioned carbon nanotubes are mutually attracted and entangled by van der Waals force to form a network structure to form a self-supporting carbon nanotube flocculation film. See Fig. 6 for a scanning electron micrograph. The aforementioned carbon nanotube film is isotropic. The above-mentioned carbon nanotube flocculation membrane can be obtained by flocculation treatment on the carbon nanotube array form number Α0101, page 9/33 page, 201137919, and can be applied to the application of Fan Shoushan et al. on May 11, 2007. And Taiwan Patent Application No. 200844041 published on November 16, 2008. In order to save space, only the above is cited, but all the technical disclosures in the aforementioned application are also considered as part of the disclosure of the technology of the present application. The aforementioned nano tube fouling film is not limited to the aforementioned preparation method. The aforementioned carbon nanotube flocculation film has a thickness of 1 micrometer to 2 millimeters. The sheet-like carbon nanotube structure 104 may include only one layer of carbon nanotube flocculation film, and its thickness is ensured to ensure better support performance. [0019] The aforementioned carbon nanotube rolled film comprises a plurality of carbon nanotubes arranged in disorder, arranged in a preferred orientation in one direction or in a preferred orientation in a complex direction, and adjacent carbon nanotubes are bonded by a van der Waals force. The carbon nanotube rolled film can be obtained by extruding the carbon nanotube array in a direction perpendicular to the substrate grown by the array of the carbon nanotubes by using a flat head, in which the carbon nanotube film is laminated. The carbon nanotubes in the disorder are arranged, and the carbon nanotube film is isotropic; the carbon nanotube membrane can also be rolled in a fixed direction by using a roller-shaped indenter. Obtained by the tube array, wherein the carbon nanotubes in the carbon nanotube film are arranged in a preferred orientation in the foregoing fixed direction; the carbon nanotube film can also be rolled in different directions by a roller-shaped indenter. Obtained in the foregoing carbon nanotube array, wherein the carbon nanotubes in the carbon nanotube rolled film are arranged in a preferred orientation in different directions. At this time, the carbon nanotube rolled film may include a plurality of portions, each portion The carbon nanotubes in the middle are arranged in a preferred orientation, and the arrangement of the carbon nanotubes in the adjacent two portions may be different. Refer to Figure 7 for the scanning electron micrograph of the aforementioned carbon nanotube rolled film. For the structure and preparation method of the above-mentioned carbon nanotube rolled film, please refer to Fan Shoushan et al., June 29, 2007, at 099112609 Form No. A0101 Page 10 of 33 0992022302-0 201137919 [0020]
G 2〇09年1月1日公開的第200900348號台灣公開專利申請 。為即省篇幅’僅引用於此，但前述中請中的所有技術 揭露也應料轉”請技術揭露的—部分。前述的奈 =碳管碾壓膜的厚度為1微米至1毫米。前述片狀奈米^ s、、’。構1G4可僅包括_層奈米碳管礙壓膜，通過調節 度來實現其具有較好的支撐性能。 ' 二管拉_複數奈米碳管組成的 J述複數奈米碳管沿同一方向擇優取向排 二擇優取向係指在奈米碳管拉膜中大多數奈米碳 不米故S的整體延伸方向基本平行於奈来破管板媒的表 面。進―步地’前述奈米碳管拉财m以管 ^凡德瓦爾力首尾㈣。具體地，前述奈米碳管拉膜中 :本朝同方向延伸的大多數奈求碳管中每一奈米碳管 連在=方向上相鄰的奈米碳管通過凡德瓦爾力首尾相 :碳奈米碳管拉膜中存在少數隨機排列的奈 乎破:^ 雜不會對奈来碳#射大多數奈 未奴^整體取轉賴成明㈣響 不需要大面積的栽想支撑，而只要二 供支撑力即能整體上懸空而保持自身膜狀狀態，即將 該奈米碳管_置於（或固定於）間隔—定距離設置的 一支推體上時，位於二切體之間的奈米碳管拉膜能夠 懸空保持自身膜狀狀態1述自支撑主要通過奈米碳管 拉膜中存在連續的通過凡德瓦爾力首尾相連延伸排列的 奈米碳管而實現。 099112609 表單編號Α0101 第11頁/共33頁 0992022302-0 201137919 [0021] 具體地，前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，可適當的彎曲；或者並 非完全按照延伸方向上排列，可適當的偏離延伸方向。 故，不能排除奈米碳管拉膜的基本朝同一方向延伸的多 數奈米碳管中並列的奈米碳管之間可能存在部分接觸。 具體地，每一奈米碳管拉膜包括複數連續且擇優取向排 列的奈米碳管片段。該複數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基本相互平行 的奈米碳管，該複數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。前述奈米碳管拉膜為從一奈米碳 管陣列中拉取獲得。根據奈米碳管陣列中奈米碳管的高 度與密度的不同，前述奈米碳管拉膜的厚度為0.5奈米 〜100微米。前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。 [0022] 當片狀奈米碳管結構104包括複數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。當片 狀奈米碳管結構中的複數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，即複數奈米碳管膜 交叉設置時，前述奈米碳管相互交織形成一網狀結構， 使前述片狀奈米碳管結構的機械性能增強。優選地，前 099112609 表單編號Α0101 第12頁/共33頁 0992022302-0 201137919 [0023] [0024] Ο [0025] Ο 099112609 述複礬奈米碳管膜交叉設置。 可以理解’複數奈米碳管膜交又設置並不要求任意兩層 相鄰的奈米碳管膜均交又設置，即允許存在相鄰兩層奈 米碳管嫉中的多數奈米碳管的排列方向相同的情形，但 優選片狀奈米石反官結構中存在至少兩層奈米碳管膜中的 多數条米碳管的排列方向之間的交叉角度大於〇度且小於 等於9〇度° 本實施例中，前述透射電鏡微栅10由前述支撐環102及片 狀奈氺破管結構1〇4組成。該支撐環102為鋼環。前述片 狀奈氺碳管結構1 〇4由複數奈米碳管線狀.結構採用平紋編 織法製備。刖述片狀奈米碳管結構的直徑為3毫米。 前述片狀奈米碳管結構104的週邊通過前述支撐環102中 的支樓環本體l〇2a及延伸部l〇2b固定》 本發明實施例提供的透射電鏡微栅1〇由前述支撐環102及 片狀条米破管結構104組成前..述.片狀奈$碳管結構1 〇4 僅遇邊通過前述未撐爭102支撐’無需金屬網格，且片狀 奈米破管結構1 〇 4為純奈米碳管結構’較為純淨，可有效 消除傳統微栅中位於被測樣品下方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微 柵1〇進行成份分析時的精確度。此外，由於本實施例中 的透射電鏡微栅10中的片狀奈米碳管結構104被前述支樓 環1〇2中的支撐環本體102a及延伸部102b固定，故，在 使用一鑷子等移動該透射電鏡微柵10時，鎖子可直接炎 持前述延伸部102b，避免鎖子與前述片狀奈米碳管結構 1〇4直接接觸，從而可避免由於片狀奈米碳管結構1〇4的 表單编號A0101 第13頁/共33頁 0992022302-0 201137919 質量較輕而引起該片狀奈米碳管結構104的飄移，同時也 減少了鑷子對片狀奈米碳管結構104的污染，進而有利於 提高採用透射電鏡對樣品進行成份分析時的精確度及解 析度。 [0026] 本實施例透射電鏡微栅10在應用時，待觀察的材料樣品 承放於前述片狀奈米碳管結構104表面。當前述材料樣品 的尺寸大於前述片狀奈米碳管結構104的微孔106時，前 述微孔106可支援該材料樣品。可通過微孔106觀測該材 料樣品。而當前述材料樣品的尺寸小於前述微孔106時， 前述材料樣品可通過片狀奈米碳管結構104中的奈米碳管 的吸附作用被穩定地吸附於奈米碳管管壁表面，此時， 亦可通過前述微孔106觀測該材料樣品。 [0027] 請參閱圖9，本發明還提供一種前述透射電鏡微柵10的製 備方法，該方法可包括以下步驟： [0028] 步驟一：提供一支撐環102。 [0029] 前述支撐環102為圓環狀，其直徑約為3毫米。前述支撐 環102的截面可為方形、圓形、半圓形或梯形等形狀。前 述支撐環102的材料可為金屬或陶瓷等。前述金屬包括銅 、翻或錄等。 [0030] 本實施例中，前述支撐環102為銅環，請參見圖2，前述 支撐環102包括一支撐環本體102a和四個延伸部102b。 前述支撐環本體102a和四個延伸部102b可為一體結構。 前述支撐環本體102a可具有一平整表面102c。前述延伸 部102b從支撐環本體102a的平整表面102c向外延伸，其 099112609 表單編號A0101 第14頁/共33頁 0992022302-0 201137919 Ο [0031] [0032] [0033] ο 延伸方向為沿延伸處與支撐環本體1〇28所在圓環的圓心 的連線方向即半徑方向。優選地，前述延伸部1〇2b與支 撐環本體102a位於同一平面内。前述延伸部1〇2b的材料 優選為具有較好的彎折性能的材料，以可實現前述延伸 部102b朝支撐環本體i〇2a圓心（支撐環本體1〇2a所在圓 環的圓心）的方向的彎折，進而固定片狀奈米碳管結構 104於前述支撐環本體1〇23與延伸部1〇2b之間。本實施 例中的延伸部l〇2b的材料與支撐環本體1〇2a的材料相同 ，均為銅。 步驟二：提供—片狀奈米碟管結構預製體，鋪設前述片 狀奈米碳管結構預製體於前述支撐環1〇2。 前述片狀奈米碳管結構預製體可由至少一奈米碳管線狀 結構編織而成或由至少一奈米碳管膜組成。 刚述奈米碳管膜可為至少一奈米碳管拉族、一奈米碳管 礙壓膜或一奈米碳管絮化膜。當前述片狀]条米碳管結構 預製體由複數奈.米..碳....管:拉膜組成時..5前述片狀奈米碳管 結構預製體可通過對複數奈米碳管拉膜廣疊且交叉設置 而形成。該奈米碳管拉膜為從一奈米碳管陣列中直接乾 法拉取獲得。前述奈米碳管拉膜的製備方法可包括以下 步驟：提供一奈来碳管陣列及從前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。 前述層疊且交又設置複數奈米碳管拉骐的少驟可具體包 括以下步驟：首先，提供—基體。該基底具有一平整表 面，其材料不限。本實施例中，該基底町為一陶瓷片。 099112609 表單編號A0101 第B頁/共33頁 0992022302-0 [0034] 201137919 其次，將前述奈米碳管拉膜依次層疊且交又鋪設於前述 基體表面。由於奈米碳管較為純淨且具有較大的比表面 積，故從奈米碳管陣列直接拉取獲得的奈米碳管拉膜具 有較好的黏性。前述奈米碳管拉膜可直接鋪設於基體表 面或另一奈米碳管拉膜表面。所謂層疊且交叉設置即於 層疊設置的奈米碳管拉膜中，複數奈米碳管拉膜中的奈 米碳管之間具有一交叉角度α且α不等於〇度。相鄰兩層 奈米碳管拉膜之間通過凡德瓦爾力緊密結合。 [0035] 前述奈米碳管線狀結構可由至少一奈米碳管線組成。當 前述奈米碳管線狀結構由複數奈米碳管線組成時，前述 奈米碳管線狀結構為複數奈米碳管線平行設置組成的一 束狀結構或複數奈米碳管線相互扭轉組成的一絞線結構 。前述奈米碳管線由複數奈米碳管組成，前述奈米碳管 線中多數奈米碳管係通過凡德瓦爾力首尾相連。前述奈 米碳管線可為一扭轉的奈米碳管線或一非扭轉的奈米碳 管線。前述片狀奈米碳管結構預製體可由複數奈米碳管 線狀結構採用平紋編織法編織而形。 [0036] 本實施例中，前述片狀奈米碳管結構預製體由複數奈米 碳管線狀結構採用平紋編織法編織而成。前述奈米碳管 線狀結構包括複數奈米碳管線平行設置組成的一束狀結 構。前述奈米碳管線及其製備方法請參見范守善等人於 2002年11月5日申請的，於2008年11月21日公告的第 1 303239號台灣公告專利，及於2005年12月16日申請， 於2009年7月21日公告的第1312337號台灣公告專利。 [0037] 前述片狀奈米碳管結構預製體可直接鋪設於前述支撐環 099112609 表單編號Α0101 第16頁/共33頁 0992022302-0 201137919 [0038] [0039] ΟG 2〇 Taiwan Public Patent Application No. 200900348, published on January 1, 2009. For the sake of the province, it is only quoted here, but all the technical disclosures in the above-mentioned proposals are also referred to the "Technical disclosure" section. The thickness of the aforementioned carbon nanotube film is 1 micron to 1 mm. Sheet-like nanometers s,, '. Structure 1G4 can only include _ layer nano carbon tube barrier film, through the degree of regulation to achieve better support performance. 'Two tube pull _ complex carbon nanotubes J. The number of carbon nanotubes in the same direction is preferred. The preferred orientation is that the majority of the carbon nanotubes in the carbon nanotube film is generally parallel to the surface of the Nylon tube. In the first step, the carbon nanotubes of the above-mentioned carbon nanotubes are used to control the end of the tube (the fourth). Specifically, in the above-mentioned carbon nanotube film, the majority of the carbon nanotubes extending in the same direction are each A carbon nanotube is connected to the adjacent carbon nanotubes in the = direction through the van der Waals force: the carbon nanotubes have a small number of randomly arranged nuclei: ^ Miscellaneous #射最奈未奴^ Overall take Lai Chengming (four) ringing does not require a large area of planting support, but as long as two support The force can be suspended in the whole to maintain its own membranous state, that is, when the carbon nanotubes are placed (or fixed) on a pusher disposed at a distance, the nanocarbon between the two cuts The tube can be suspended to maintain its own membranous state. The self-supporting is mainly realized by the presence of continuous carbon nanotubes extending through the end of the van der Waals force in the carbon nanotube film. 099112609 Form No. 1010101 Page 11 / Total 33 pages 0992022302-0 201137919 [0021] Specifically, most of the carbon nanotubes extending in the same direction in the aforementioned carbon nanotube film are not absolutely linear, and may be appropriately bent; or not completely in accordance with the extending direction The upper arrangement may be appropriately deviated from the extending direction. Therefore, it may not be possible to exclude partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes extending substantially in the same direction of the carbon nanotube film. Specifically, each The carbon nanotube film comprises a plurality of carbon nanotube segments arranged in a continuous and preferential orientation. The plurality of carbon nanotube segments are connected end to end by Van der Waals force. The plurality of carbon nanotubes are substantially parallel to each other, and the plurality of substantially parallel carbon nanotubes are closely coupled by van der Waals force. The carbon nanotube segments have arbitrary length, thickness, uniformity and shape. The carbon nanotubes in the tube are arranged in a preferred orientation in the same direction. The aforementioned carbon nanotube film is drawn from an array of carbon nanotubes. According to the height of the carbon nanotubes in the carbon nanotube array The thickness of the carbon nanotube film is 0.5 nm to 100 μm, and the width of the carbon nanotube film is related to the size of the carbon nanotube array for pulling the carbon nanotube film. The length is not limited. [0022] When the sheet-shaped carbon nanotube structure 104 includes a plurality of carbon nanotube films and the carbon nanotubes in each of the carbon nanotube films are aligned in the same direction, the adjacent two layers are The arrangement of the carbon nanotubes in the 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 sheet-shaped carbon nanotube structure have an intersection angle α and α is not equal to 0 degrees, that is, when the plurality of carbon nanotube membranes are disposed at the intersection, the aforementioned nai The carbon nanotubes are interwoven to form a network structure, which enhances the mechanical properties of the aforementioned sheet-like carbon nanotube structure. Preferably, the first 099112609 form number Α0101 page 12/total page 33 0992022302-0 201137919 [0023] 00 [0025] Ο 099112609 The resurfacing nano carbon tube film cross setting. It can be understood that the 'multiple carbon nanotube film intersection and setting does not require any two adjacent layers of carbon nanotube film to be evenly disposed, that is, the majority of the carbon nanotubes in the adjacent two layers of carbon nanotubes are allowed to exist. The arrangement direction is the same, but it is preferable that the intersection angle between the arrangement directions of the plurality of carbon nanotubes in the at least two layers of the carbon nanotube film in the reticular structure of the sheet-like nano-steel is greater than the twist and less than or equal to 9〇. In the present embodiment, the TEM microgrid 10 is composed of the support ring 102 and the sheet-shaped nai tube structure 1〇4. The support ring 102 is a steel ring. The above-mentioned sheet-shaped carbon nanotube structure 1 〇 4 is composed of a plurality of carbon nanotubes. The structure is prepared by a plain weave method. The sheet-like carbon nanotube structure has a diameter of 3 mm. The periphery of the sheet-like carbon nanotube structure 104 is fixed by the support ring body l〇2a and the extension portion 〇2b in the support ring 102. The TEM micro-gate 1 provided by the embodiment of the present invention is supported by the support ring 102. And the sheet-shaped strip-breaking tube structure 104 is composed of the front part.. described. The sheet-shaped nai$ carbon tube structure 1 〇4 only encounters the side through the aforementioned unsupported 102 support 'no metal grid, and the sheet-like nano-tube structure 1 〇4 is a pure carbon nanotube structure's purer, which can effectively eliminate the interference of the metal grid under the sample under the sample in the traditional micro-grid to analyze the composition of the sample being tested', which is beneficial to improve the transmission micro-grid. Accuracy when performing component analysis. In addition, since the sheet-shaped carbon nanotube structure 104 in the TEM microgrid 10 in the present embodiment is fixed by the support ring body 102a and the extension portion 102b in the above-mentioned branch ring 1〇2, a dice or the like is used. When the TEM microgrid 10 is moved, the lock can directly hold the extension portion 102b to prevent the lock from directly contacting the sheet-like carbon nanotube structure 1〇4, thereby avoiding the sheet-like carbon nanotube structure 1 Form No. A0101 of 〇4 Page 13 of 33 0992022302-0 201137919 The lighter mass causes the drift of the sheet-like carbon nanotube structure 104, and also reduces the hazelnut-to-sheet carbon nanotube structure 104. Contamination, in turn, is conducive to improving the accuracy and resolution of component analysis using TEM. In the present embodiment, the TEM microgrid 10 is applied to the surface of the sheet-like carbon nanotube structure 104 when it is applied. When the size of the aforementioned material sample is larger than the micropores 106 of the sheet-like carbon nanotube structure 104, the micropores 106 can support the material sample. The material sample can be observed through the microholes 106. When the size of the material sample is smaller than the micropores 106, the material sample can be stably adsorbed on the surface of the carbon nanotube wall through the adsorption of the carbon nanotubes in the sheet-shaped carbon nanotube structure 104. The material sample can also be observed through the aforementioned micropores 106. Referring to FIG. 9, the present invention further provides a method for preparing the TEM micro-gate 10, which may include the following steps: [0028] Step 1: Provide a support ring 102. [0029] The aforementioned support ring 102 is annular and has a diameter of about 3 mm. The cross section of the aforementioned support ring 102 may be in the shape of a square, a circle, a semicircle or a trapezoid. The material of the support ring 102 described above may be metal or ceramic or the like. The foregoing metals include copper, turn or record, and the like. [0030] In this embodiment, the support ring 102 is a copper ring. Referring to FIG. 2, the support ring 102 includes a support ring body 102a and four extension portions 102b. The aforementioned support ring body 102a and the four extensions 102b may be a unitary structure. The aforementioned support ring body 102a may have a flat surface 102c. The aforementioned extension portion 102b extends outwardly from the flat surface 102c of the support ring body 102a, which is 099112609 Form No. A0101 Page 14 / Total 33 Page 0992022302-0 201137919 Ο [0031] [0033] ο The extension direction is along the extension The direction of the line connecting the center of the ring in which the support ring body 1〇28 is located is the radial direction. Preferably, the aforementioned extensions 1〇2b are in the same plane as the support ring body 102a. The material of the extending portion 1〇2b is preferably a material having a good bending property, so that the direction of the extending portion 102b toward the center of the supporting ring body i〇2a (the center of the ring in which the ring body 1〇2a is supported) can be realized. The bending is performed to fix the sheet-like carbon nanotube structure 104 between the support ring body 1〇23 and the extension 1〇2b. The material of the extension portion 〇2b in this embodiment is the same as that of the support ring body 1 〇 2a, and is copper. Step 2: providing a sheet-like nano-disc structure preform, and laying the aforementioned sheet-shaped carbon nanotube structure preform on the aforementioned support ring 1〇2. The sheet-like carbon nanotube structure preform may be woven from at least one nanocarbon line structure or composed of at least one carbon nanotube film. The carbon nanotube membrane can be at least one carbon nanotube, one nanocarbon tube or one carbon tube. When the pre-formed body of the sheet-like] carbon nanotube structure is composed of a plurality of nanometers.. carbon: tube: a film is formed, the above-mentioned sheet-like carbon nanotube structure preform can pass through a plurality of nanocarbons The tube is formed by stacking and stacking. The carbon nanotube film is obtained by direct dry extraction from a carbon nanotube array. The preparation method of the aforementioned carbon nanotube film may include 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. The foregoing steps of laminating and placing a plurality of carbon nanotubes may specifically include the following steps: First, a substrate is provided. The substrate has a flat surface and the material is not limited. In this embodiment, the base town is a ceramic sheet. 099112609 Form No. A0101 Page B/Total 33 0992022302-0 [0034] 201137919 Next, the above-mentioned carbon nanotube film is laminated in this order and laid on the surface of the aforementioned substrate. Since the carbon nanotubes are relatively pure and have a large specific surface area, the carbon nanotube film obtained by directly pulling from the carbon nanotube array has good viscosity. The aforementioned carbon nanotube film can be directly laid on the surface of the substrate or the surface of the other carbon nanotube film. The so-called lamination and cross-setting means that in the laminated carbon nanotube film, the carbon nanotubes in the plurality of carbon nanotube films have an intersection angle α and α is not equal to the twist. Adjacent two layers of carbon nanotube film are tightly bonded by van der Waals force. [0035] The aforementioned nanocarbon line-like structure may be composed of at least one nano carbon line. When the aforementioned nanocarbon pipeline-like structure is composed of a plurality of nano carbon pipelines, the aforementioned nanocarbon pipeline-like structure is a bundle structure in which a plurality of nano carbon pipelines are arranged in parallel or a twist of a plurality of nanocarbon pipelines twisted together Line structure. The aforementioned nano carbon pipeline is composed of a plurality of carbon nanotubes, and most of the carbon nanotubes in the aforementioned carbon nanotubes are connected end to end by Van der Waals force. The aforementioned carbon carbon line may be a twisted nanocarbon line or a non-twisted nano carbon line. The aforementioned sheet-like carbon nanotube structure preform may be formed by weaving a plurality of carbon nanotube linear structures by a plain weave method. [0036] In the embodiment, the sheet-like carbon nanotube structure preform is woven by a plain carbon weave structure by a plain weave method. The aforementioned carbon nanotube linear structure includes a bundle structure in which a plurality of carbon nanotubes are arranged in parallel. For the above-mentioned nano carbon pipeline and its preparation method, please refer to the patent issued by Fan Shoushan et al. on November 5, 2002, published on November 21, 2008, No. 1 303239, and filed on December 16, 2005. , Taiwan No. 1312337 announced on July 21, 2009 announced the patent. [0037] The aforementioned sheet-shaped carbon nanotube structure preform can be directly laid on the aforementioned support ring 099112609 Form No. 1010101 Page 16 of 33 0992022302-0 201137919 [0038] [0039]
102表面。當前述支撐環102具有一平整表面時，前述片 狀奈米碳管結構預製體可直接鋪設於前述支撐環102的平 整表面。本實施例中，前述片狀奈米碳管結構預製體可 直接鋪設於前述支撐環本體102a的平整表面102c。 步驟三：按預定尺寸切割前述片狀奈米碳管結構預製體 ，形成前述片狀奈米碳管結構104。 前述按預定尺寸切割前述片狀奈米碳管結構預製體的步 驟具體包括以下步驟：提供一聚焦雷射光束；將該聚焦 雷射光束照射至前述片狀奈米碳管結構預製體表面；及 按照支撐環的形狀即支撐環本體10 2 a外週沿進行切割， 切割後的片狀奈米碳管結構104的週邊通過前述支撐環 102支撐，片狀奈米碳管結構104的中心部分懸空設置。 具體地，前述片狀奈米碳管結構104的週邊固定於前述支 撐環本體102a與至少一延伸部102b之間。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5〜3 0瓦（W)，優選為18W。具體地，該雷 射光束可通過一透鏡聚焦後從正面直接照射於前述片狀 奈米碳管結構預製體表面，可以理解，該雷射光束可採 用垂直照射或傾斜照射聚焦於前述片狀奈米碳管結構預 製體表面。前述片狀奈米碳管結構預製體可吸收雷射光 束的能量從而與空氣中的氧發生反應並分解，從而使具 有預定尺寸的片狀奈米碳管結構預製體與其他部分斷開 。本實施例中，切割後所形成的片狀奈米碳管結構104為 圓片狀，其週邊固定於前述支撐環本體102a與至少一延 伸部102b之間，所形成的片狀奈米碳管結構104的直徑約 099112609 表單編號A0101 第17頁/共33頁 0992022302-0 201137919 為3毫米。 [0040] 前述切割步驟可採用固定前述片狀奈米碳管結構預製體 ，移動雷射光束；或固定雷射光束，移動前述片狀奈米 碳管結構預製體的方式來實現。本實施例並不限於前述 雷射處理方法，先前技術中的其他方法，如物理或化學 蝕刻法，同樣可用於切割前述片狀奈米碳管結構預製體 〇 [0041] 步驟四：固定前述片狀奈米碳管結構104於前述支撐環 102 ° [0042] 前述片狀奈米碳管結構104可通過黏結劑、凡德瓦爾力， 採用機械方式，或前述任意兩種或多種方式的結合固定 於前述支撐環102。 [0043] 當採用黏結劑方式固定時，進一步包括在鋪設前述片狀 奈米碳管結構預製體於前述支撐環表面之前，塗覆一層 黏結劑於前述支撐環的表面，及在切割前述片狀奈米碳 管結構預製體，形成一片狀奈米碳管結構104之後，固化 前述黏結劑，進而固定前述片狀奈米碳管結構104於前述 支撐環102。 [0044] 當採用凡德瓦爾力方式固定時，前述片狀奈米碳管結構 104可通過自身的黏性或通過有機溶劑處理直接鋪設於前 述支撐環102的表面。當採用有機溶劑處理方式固定時， 前述有機溶劑優選為揮發性有機溶劑，此時，可將揮發 性有機溶劑滴落於鋪設有片狀奈米碳管結構104的支撐環 102表面，在揮發性有機溶劑的作用下，片狀奈米碳管結 099112609 表單編號A0101 第18頁/共33頁 0992022302-0 201137919 [0045] 構104通過凡德瓦爾力更緊密地貼合固定於前述支撐埽 102的表面，實現固定。可以理解，前述片狀奈米碳管社 構104與前述支撐環102之間的固定並不限於前述方式。 本實施例中’可通過將前述四個延伸部l〇2b朝支偉导1〇2 圓心的方向彎折，使其覆蓋位於支撐環本體1〇2a的平整 表面102c的片狀奈米碳管結構1〇4，來實現片狀奈米唉其 結構104固疋於刚述支撑ί哀本體i〇2a與四個延伸部 之間。 Ο [0046] 進一步地，可採用有機溶劑處理前述駕狀奈米碳管結構 預製體或片狀奈米碳管結構1〇4的步驟。該有機溶劑為常 溫下易揮發的有機溶劑，可選用乙醇、甲醇、丙綱、_ Ο 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 的满濕性。該使用有機_處理的步㈣體為：通過^ 管將有機溶劑祕於片狀奈米碳管結構預製體或片狀奈 米碳管結構1()4表面，或將、固定後的片狀奈米碳管結構 104與支推環102浸政盛有有機溶劑的容器中制。有機 溶劑處理後，片狀奈米碳管結構預製體或片狀奈米碳管 結構104中部分相鄰的奈米碳管會聚集形成奈来碳管束， 片狀奈米碳管線狀結構表面具有自由端的奈米碳管會貼 合於奈米碳管線狀結構表面。料 1〇4包括複數奈米碳管拉膜，且相鄰兩層奈米碳管拉膜中 的奈米碳管具有-交又角度α，且〜㈣。時有機溶 劑處理後的奈㈣管拉財料管束相互交叉，從 而形成複數微孔106。該微孔1η 的尺寸小於1〇微米。可 099112609 表單編號A0101 第19頁/共33頁 0992022302-0 201137919 以理解，進一步地，通過有機溶劑處理還可使該片狀奈 米碳管結構預製體或片狀奈米碳管結構1〇4與支撐環 結合緊密，從而使該片狀奈米碳管結構預製體或片狀奈 米碳管結構104更牢固地固定於該支撐環1〇2上。 [0047] [0048] 可以理解，前述步驟可通過鋪設一較大尺寸的片狀奈米 碳管結構預製體於複數支撐環102表面，並按支撐環1〇2 的形狀即支撐環本體丨02&的外週沿切割前述片狀奈米碳 管結構預製體，來實現快速批量生產透射電鏡微柵1〇。 本發明實施例提供的透射電鏡微栅及其製備方法具有以 下優點：其一，前述透射電鏡微栅由一支撐環及—片狀 奈米碳管結構組成，片狀奈米碳管結構僅週邊通過前述 支撐環固定，無需金屬網格，且片狀奈米碳管結構為純 奈米碳管結構，可有效消除傳統微栅中的位於被測樣品 下方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威份分析時的精確度。其二 ，由於本發明實施例透射電鏡薄部中的片狀奈米碳管結 構被前述支撐環中的支撐環本體及延伸部固定，故在 使用鑷子等移動該透射電鏡微栅時，鑷子可直接夾持前 述延伸部，避免鑷子與前述片狀奈米碳管結構直接接觸 ，從而可避免由於片狀奈米碳管結構的質量較輕而引起 該片狀奈来碳官結構的飄移，同時也減少了鑷子對片狀 奈米碳管結構的污染，進而有利於提高採用透射電鏡對 樣品進行成份分析時的精確度及解析度。其三，本發明 實施例提供的透射電鏡微柵通過提供一支撐環及—片狀 奈米碳管結構預製體，將該片狀奈米碳管結構預製體鋪 099112609 表單編號A0101 第20頁/共33頁 0992022302-0 201137919 [0049] Ο [0050] [0051] [0052] [0053] ❹ [0054] [0055] [0056] [0057] 099112609 又於别述支撑環，及將切割後的片狀奈米碳管結構預製 體固定於支撐環來製備，無需蒸鍍過程，故，製備方法 較為簡單》 综上所述，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】 .: . . .... .. ........ . 圖1為本發明實施例透射電鏡微栅的立體結構示意圖。 圖2為本發明實施例透射電鏡微柵中的支撐環的立體結構 示意圖。 圖3為本發明實施例透射電鏡微柵中的支撐環的剖視結構 不意圖。 圖4為本發明實施例透射電練缉柵中的非扭轉的奈米碳管 線的掃据電鏡照片: 圖5為本發明實施例透射電鏡微柵中的扭轉的奈米碳管線 的掃描電鏡照片。 圖6為本發明實施例透射電鏡微柵中的奈米碳管絮化膜的 掃插電鏡照片。 圖7為本發明實施例透射電鏡微栅中的奈米碳管礙壓膜的 掃描電鏡照片。 圖8為本發明實施例透射電鏡微柵中的奈米碳管拉膜的掃 第21頁/共33頁 &單鵝號Α0101 0992022302-0 201137919 描電鏡照片。 [0058] 圖9為本發明實施例透射電鏡微柵的製備方法的流程示意 圖。 【主要元件符號說明】 [0059] 透射電鏡微栅：10 [0060] 支撐環：102 [0061] 支撐環本體：102a [0062] 延伸部：102b [0063] 片狀奈米碳管結構：104 [0064] 微孔：106 0992022302-0 099112609 表單編號A0101 第22頁/共33頁102 surface. When the aforementioned support ring 102 has a flat surface, the aforementioned sheet-like carbon nanotube structure preform can be directly laid on the flat surface of the aforementioned support ring 102. In this embodiment, the sheet-like carbon nanotube structure preform can be directly laid on the flat surface 102c of the support ring body 102a. Step 3: cutting the aforementioned sheet-shaped carbon nanotube structure preform to a predetermined size to form the sheet-like carbon nanotube structure 104. The step of cutting the foregoing sheet-shaped carbon nanotube structure preform according to a predetermined size specifically includes the steps of: providing a focused laser beam; and irradiating the focused laser beam to the surface of the sheet-like carbon nanotube structure preform; The outer circumferential edge of the support ring body 10 2 a is cut according to the shape of the support ring, and the periphery of the cut sheet-shaped carbon nanotube structure 104 is supported by the support ring 102, and the central portion of the sheet-shaped carbon nanotube structure 104 is suspended. Settings. Specifically, the periphery of the sheet-like carbon nanotube structure 104 is fixed between the support ring body 102a and the at least one extending portion 102b. In this embodiment, the laser beam can be generated by a conventional argon ion laser or carbon dioxide laser having a power of 5 to 30 watts (W), preferably 18 watts. Specifically, the laser beam can be directly focused on the surface of the sheet-like carbon nanotube structure preform 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 navel by vertical illumination or oblique illumination. The carbon nanotube structure prefabricated body surface. The aforementioned sheet-like carbon nanotube structure preform absorbs the energy of the laser beam to react with and decomposes with oxygen in the air, thereby disconnecting the sheet-shaped carbon nanotube structure preform having a predetermined size from the other portions. In this embodiment, the sheet-shaped carbon nanotube structure 104 formed after cutting is in the form of a disk, and the periphery thereof is fixed between the support ring body 102a and the at least one extending portion 102b, and the formed sheet of carbon nanotubes is formed. The diameter of the structure 104 is approximately 099112609. Form number A0101 Page 17 of 33 page 0992022302-0 201137919 is 3 mm. [0040] The cutting step may be implemented by fixing the aforementioned sheet-shaped carbon nanotube structure preform, moving the laser beam, or fixing the laser beam, and moving the sheet-shaped carbon nanotube structure preform. This embodiment is not limited to the aforementioned laser processing method, and other methods in the prior art, such as physical or chemical etching, can also be used to cut the aforementioned sheet-like carbon nanotube structure preforms [0041] Step 4: Fix the aforementioned sheet The carbon nanotube structure 104 is in the aforementioned support ring 102 ° [0042] The sheet-like carbon nanotube structure 104 can be fixed by a bonding agent, a van der Waals force, mechanically, or a combination of any two or more of the foregoing. In the aforementioned support ring 102. [0043] when the adhesive is used for fixing, further comprising coating a surface of the support ring on the surface of the support ring before laying the sheet-like carbon nanotube structure preform on the surface of the support ring, and cutting the sheet shape The carbon nanotube structure preform forms a sheet of carbon nanotube structure 104, and then cures the binder to fix the sheet-like carbon nanotube structure 104 to the support ring 102. When the van der Waals force is used for fixing, the sheet-like carbon nanotube structure 104 can be directly laid on the surface of the support ring 102 by its own viscosity or by an organic solvent treatment. When the organic solvent treatment is used for immobilization, the organic solvent is preferably a volatile organic solvent. At this time, the volatile organic solvent may be dropped on the surface of the support ring 102 on which the sheet-shaped carbon nanotube structure 104 is laid. Sheet-shaped carbon nanotube knots under the action of organic solvents 099112609 Form No. A0101 Page 18 of 33 0992022302-0 201137919 [0045] The structure 104 is more closely attached to the support 埽102 by the Van der Waals force. Surface, fixed. It will be understood that the fixation between the aforementioned sheet-like carbon nanotube structure 104 and the aforementioned support ring 102 is not limited to the foregoing. In the present embodiment, the sheet-shaped carbon nanotubes located on the flat surface 102c of the support ring body 1〇2a can be covered by bending the aforementioned four extension portions 10b to the center of the support guide 1〇2. The structure 1〇4 is used to realize the sheet-like nano-rhodium whose structure 104 is fixed between the support body 〇2a and the four extensions. Further, the step of treating the aforementioned carbon nanotube structure preform or sheet-like carbon nanotube structure 1〇4 with an organic solvent may be employed. The organic solvent is an organic solvent which is volatile at normal temperature, and may be selected from a mixture of one or more of ethanol, methanol, propylene, hexane, and gas. The organic solvent in this embodiment is ethanol. The organic solvent should have good full wettability with the carbon nanotubes. The step (4) of using the organic_treatment is: the organic solvent is secreted by the tube to the surface of the sheet-like carbon nanotube structure preform or the sheet-like carbon nanotube structure 1 () 4, or the sheet after the fixation The carbon nanotube structure 104 and the push ring 102 are immersed in a container containing an organic solvent. After the organic solvent treatment, some adjacent carbon nanotubes in the sheet-shaped carbon nanotube structure preform or the sheet-shaped carbon nanotube structure 104 are aggregated to form a Neilite tube bundle, and the sheet-like nanocarbon line-like structure surface has The free end of the carbon nanotubes will conform to the surface of the nanocarbon line structure. The material 1〇4 includes a plurality of carbon nanotube film, and the carbon nanotubes in the adjacent two layers of carbon nanotube film have an intersection angle α and a value of (4). When the organic solvent is treated, the neat (four) tube pull bundles cross each other to form a plurality of micropores 106. The size of the micropores 1n is less than 1 μm. 099112609 Form No. A0101 Page 19 of 33 0992022302-0 201137919 It is understood that, further, the sheet-like carbon nanotube structure preform or sheet-like carbon nanotube structure can be made by organic solvent treatment. The sheet is tightly coupled to the support ring so that the sheet-like carbon nanotube structure preform or sheet-like carbon nanotube structure 104 is more firmly fixed to the support ring 1〇2. [0048] It can be understood that the foregoing steps can be prefabricated on the surface of the plurality of support rings 102 by laying a large-sized sheet-shaped carbon nanotube structure, and in the shape of the support ring 1〇2, that is, the support ring body 丨02& The outer peripheral edge cuts the aforementioned sheet-shaped carbon nanotube structure preform to realize rapid mass production of the transmission electron microstrip microgrid. 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 support ring and a sheet-like carbon nanotube structure, and the sheet-like carbon nanotube structure is only surrounding The support ring is fixed by the foregoing support ring, and the metal mesh is not needed, and the sheet-shaped carbon nanotube structure is a pure carbon nanotube structure, which can effectively eliminate the metal mesh of the traditional micro-grid under the sample to be tested. Time interference, which is beneficial to improve the accuracy of the transmission analysis using the transmission electron microscope. Secondly, since the sheet-shaped carbon nanotube structure in the thin portion of the TEM of the embodiment of the present invention is fixed by the support ring body and the extension portion in the support ring, when the TEM is used to move the TEM micro-gate, the raft can be used. Directly clamping the extension portion to avoid direct contact between the rafter and the sheet-like carbon nanotube structure, thereby avoiding the drift of the sheet-like carbonaceous structure due to the light weight of the sheet-like carbon nanotube structure, and simultaneously It also reduces the contamination of the sheet-like carbon nanotube structure by the scorpion, which is beneficial to improve the accuracy and resolution of the sample analysis by TEM. Thirdly, the TEM micro-gate provided by the embodiment of the present invention provides a support ring and a sheet-shaped carbon nanotube structure preform, and the sheet-shaped carbon nanotube structure prefabricated body is paved. 099112609 Form No. A0101 Page 20 / A total of 33 pages 0992022302-0 201137919 [0049] [0052] [0055] [0055] [0057] [0057] 099112609 and other support rings, and the slice after cutting The carbon nanotube structure prefabricated body is fixed on the support ring to prepare, and the evaporation process is not required, so the preparation method is relatively simple. 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, and it is not possible to limit the scope of the patent application 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 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 schematic perspective view showing a support ring of a transmission electron microscope micro-gate according to an embodiment of the present invention. Fig. 3 is a cross-sectional view showing the structure of a support ring in a TEM microgrid according to an embodiment of the present invention. 4 is a scanning electron micrograph of a non-twisted nanocarbon pipeline in a transmission electro-precision grid according to an embodiment of the present invention: FIG. 5 is a scanning electron micrograph of a twisted nanocarbon pipeline in a TEM microgrid according to an embodiment of the present invention; . Fig. 6 is a scanning electron micrograph of a carbon nanotube flocculation film in a TEM microgrid according to an embodiment of the present invention. Fig. 7 is a scanning electron micrograph of a carbon nanotube barrier film in a TEM microgrid according to an embodiment of the present invention. 8 is a scanning electron micrograph of a carbon nanotube film in a TEM microgrid according to an embodiment of the present invention. Page 21 of 33 & single goose Α0101 0992022302-0 201137919. 9 is a schematic flow chart showing a method of fabricating a TEM microgate according to an embodiment of the present invention. [Major component symbol description] [0059] Transmission electron microstrip: 10 [0060] Support ring: 102 [0061] Support ring body: 102a [0062] Extension: 102b [0063] Sheet-shaped carbon nanotube structure: 104 [ 0064] Micropores: 106 0992022302-0 099112609 Form No. A0101 Page 22 of 33