TWI411572B - Transmission electron microscope grid and method for making same - Google Patents

Transmission electron microscope grid and method for making same Download PDF

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TWI411572B
TWI411572B TW98126005A TW98126005A TWI411572B TW I411572 B TWI411572 B TW I411572B TW 98126005 A TW98126005 A TW 98126005A TW 98126005 A TW98126005 A TW 98126005A TW I411572 B TWI411572 B TW I411572B
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carbon nanotube
graphene sheet
nanotube film
composite structure
grid
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TW201103862A (en
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Kai-Li Jiang
Li-Na Zhang
Hao-Xu Zhang
Shou-Shan Fan
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Hon Hai Prec Ind Co Ltd
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Abstract

The invention relates to a transmission electron microscope grid. The transmission electron microscope grid includes a grid, and a graphene sheet-carbon nanotube film composite structure covered on the grid. A part of the composite structure are suspended. The composite structure includes at least a carbon nanotube film structure and a plurality of graphene sheets. The carbon nanotube film structure includes a plurality of micropores. At least one micropore of the carbon nanotube film structure is covered by one of the plurality of graphene sheets. The present invention also relates to a method for making the transmission electron microscope grid.

Description

透射電鏡微栅及其製備方法Transmission electron micro-gate and preparation method thereof

本發明涉及一種透射電鏡微栅及其製備方法。The invention relates to a transmission electron microscope microgrid and a preparation method thereof.

在透射電子顯微鏡中,非晶碳支持膜(微栅)係用於承載粉末樣品,進行透射電子顯微鏡高分辨像(HRTEM)觀察的重要工具。隨著奈米材料研究的不斷發展,微栅在奈米材料的電子顯微學表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。In transmission electron microscopy, an amorphous carbon support film (microgrid) is an important tool for carrying powder samples for high-resolution image observation (HRTEM) observation by transmission electron microscopy. 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 amorphous carbon film in the micro-gate is thicker, the contrast noise is larger, and the transmission electron microscope imaging of the nano-particles is performed. The increase in resolution has a great impact.

有鑒於此,提供一種透射電鏡微栅及其製備方法,其中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。In view of the above, a TEM micro-grid and a preparation method thereof are provided, wherein the TEM micro-gate is more effective for nano-scale particles, and it is more necessary to obtain a high-resolution image of a transmission electron microscope.

一種透射電鏡微栅,其包括一網格以及一石墨烯片-奈米碳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烯片,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。A TEM microgrid comprising a grid and a graphene sheet-nanocarbon tube membrane composite structure covering the grid, and the grid portion is suspended by the grid portion, the graphene sheet-nanocarbon tube membrane composite structure The method includes at least one carbon nanotube film structure and a plurality of graphene sheets, and the carbon nanotube film structure comprises a plurality of micropores, wherein at least one micropores are covered by a graphene sheet.

一種透射電鏡微栅,其包括一網格,以及一石墨烯片-奈米碳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烯片,該奈米碳管膜結構包括多個奈米碳管線交叉設置以及由該多個交叉設置的奈米碳管線形成的多個微孔,其中,至少一微孔被一石墨烯片覆蓋。A TEM microgrid comprising a grid, and a graphene sheet-nanocarbon tube membrane composite structure covering the grid, and being suspended by the grid portion, the graphene sheet-nanocarbon tube membrane composite The structure comprises at least one carbon nanotube film structure and a plurality of graphene sheets, wherein the carbon nanotube membrane structure comprises a plurality of nano carbon pipeline crossovers and a plurality of micros formed by the plurality of intersecting nanocarbon pipelines a hole, wherein at least one of the micropores is covered by a graphene sheet.

一種透射電鏡微栅的製備方法,其包括以下步驟:提供一自支撑的奈米碳管膜結構,以及一石墨烯片分散液,該奈米碳管膜結構包括多個微孔;將該石墨烯片分散液浸潤該奈米碳管膜結構表面;乾燥該被石墨烯片浸潤的奈米碳管膜結構,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;以及將所述石墨烯片-奈米碳管膜複合結構覆蓋一網格。A method for preparing a transmission electron microstrip microgate, comprising the steps of: providing a self-supporting carbon nanotube film structure, and a graphene sheet dispersion comprising a plurality of micropores; the graphite The olefin dispersion disperses the surface of the carbon nanotube film structure; drying the carbon nanotube film structure infiltrated by the graphene sheet, thereby compounding the graphene sheet with the carbon nanotube film structure to form a graphene sheet a carbon nanotube film composite structure; and covering the graphene sheet-carbon nanotube film composite structure with a grid.

相較於先前技術,所述的透射電鏡微栅及其製備方法,通過從奈米碳管陣列拉取獲得奈米碳管膜結構,並將該奈米碳管膜結構作爲一種具有微孔的支撑骨架,通過將石墨烯片覆蓋在該支撑骨架的微孔上,實現石墨烯片的懸空設置。由於石墨烯片具有極薄的厚度,在透射電鏡觀察中産生的襯度噪聲較小,從而可獲得分辨率較高的透射電鏡照片。Compared with the prior art, the TEM microgrid and the preparation method thereof are obtained by extracting a carbon nanotube film structure from a carbon nanotube array, and using the carbon nanotube film structure as a microporous structure. Supporting the skeleton, the dangling arrangement of the graphene sheets is achieved by covering the micropores of the support skeleton with graphene sheets. Since the graphene sheets have an extremely thin thickness, the contrast noise generated in the transmission electron microscope observation is small, so that a TEM photograph with a higher resolution can be obtained.

下面將結合附圖及具體實施例對本發明提供的透射電鏡微栅及其製備方法作進一步的詳細說明。The TEM micro-gate and the preparation method thereof provided by the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

請參閱圖1,本發明第一實施例透射電鏡微栅的製備方法主要包括以下幾個步驟:Referring to FIG. 1, a method for preparing a TEM micro-gate according to a first embodiment of the present invention mainly includes the following steps:

步驟一,提供一奈米碳管膜結構,以及一石墨烯片分散液。In the first step, a carbon nanotube film structure and a graphene sheet dispersion are provided.

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:The carbon nanotube membrane structure comprises a plurality of layers of cross-laminated carbon nanotube membranes. The carbon nanotube film is obtained by directly pulling from a carbon nanotube array, and the preparation method thereof comprises the following steps:

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。First, an array of carbon nanotubes is provided on a growth substrate that is a super-aligned array of carbon nanotubes.

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。The carbon nanotube array is prepared by chemical vapor deposition, and the carbon nanotube array is a plurality of pure carbon nanotube arrays formed by carbon nanotubes which are parallel to each other and perpendicular to the growth substrate. Through the above 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 drawing 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 micrometers to 900 micrometers.

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。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, thereby forming a continuous carbon nanotube film. The pull direction is substantially perpendicular to the growth direction of the nanotube array.

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。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 respectively combined with the other due to the van der Waals force. The carbon nanotube segments are continuously drawn end to end to form a continuous, uniform, self-supporting carbon nanotube film having a 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 method of directly stretching to obtain a carbon nanotube film is simple and rapid, and is suitable for industrial application.

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~100微米。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. When the area of the carbon nanotube array is 4 inches, the width of the carbon nanotube film is 3 mm to 10 cm, and the thickness of the carbon nanotube film is 0.5 nm to 100 μm.

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,中部懸空設置。It can be understood that the preparation method of 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, so that it is repeated several times. A plurality of carbon nanotube membranes are laid on the frame. The plurality of carbon nanotube films may be laid in different directions or may be laid only in two intersecting directions. It can 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, and the middle portion is suspended.

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。Since the carbon nanotube film has a large specific surface area, the carbon nanotube film has a large viscosity, so the multilayer carbon nanotube film can be closely combined with each other to form a stable carbon nanotube through the van der Waals force. Membrane structure. In the carbon nanotube membrane structure, the number of layers of the carbon nanotube membrane is not limited, and the adjacent two layers of carbon nanotube membranes 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 to 4 layers. .

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。After the above-described carbon nanotube film structure is formed, the carbon nanotube film structure may be further treated with an organic solvent to form a plurality of micropores in the carbon nanotube film structure.

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、二氯乙烷和氯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滴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°,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。The organic solvent is a volatile organic solvent at normal temperature, and one or a mixture of ethanol, methanol, acetone, dichloroethane and chloroform may be used. The organic solvent in this embodiment is ethanol. The organic solvent should have good wettability with the carbon nanotube. The step of treating with an organic solvent is specifically: infiltrating the entire 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 membranes have a crossing angle α and 0<α≦90°, the nanocarbon pipelines in the adjacent two layers of carbon nanotube membranes after the organic solvent treatment are mutually Crossing 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 micropores having a size of nanometers in the nanocarbon membrane membrane structure can reach 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.

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。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 other methods of dispersing the graphene sheet may be employed, such as stirring the mixture of the graphene sheet and the solvent by mechanical agitation.

該溶劑應選擇爲利於石墨烯片分散,且能够完全揮發的低分子量溶劑,如水、乙醇、甲醇、丙酮、二氯乙烷和氯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。The solvent should be selected as a low molecular weight solvent which is advantageous for the dispersion of graphene sheets and which is completely volatile, such as a mixture of one or more of water, ethanol, methanol, acetone, dichloroethane and chloroform. In this embodiment, the solvent is water. It can be understood that the solvent only functions 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.

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。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 1-3 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 microns or less and may be less than 1 micron. The graphene sheet has a concentration of 5% (volume percentage) or less in the sample dispersion to be tested.

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。In step two, the graphene sheet dispersion is impregnated onto the surface of the carbon nanotube membrane structure.

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,如將整個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。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 of the carbon nanotube membrane is large, the whole carbon nanotube membrane structure can be immersed in the graphene sheet dispersion by other means, and the carbon nanotube membrane structure can be further Removed from the graphene sheet dispersion.

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。In the present embodiment, a carbon nanotube film structure infiltrated by the graphene sheet dispersion is formed on the frame by dropping a graphene sheet dispersion onto the surface of the carbon nanotube film structure laid on the frame.

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過石墨烯片分散液浸潤的表面,形成一夾心結構。After infiltrating the carbon nanotube film structure by the graphene sheet dispersion, another nano carbon tube film structure may be further covered on the surface of the above-mentioned carbon nanotube film structure infiltrated by the graphene sheet dispersion to form a sandwich structure. .

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烯片分散液相間層叠。本實施例中,該夾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。It will be appreciated that the other carbon nanotube membrane structure may comprise a single or multiple layer of carbon nanotube membranes, which 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, thereby forming a multilayer sandwich. structure. The multilayer sandwich structure comprises a multilayered carbon nanotube film structure laminated with a plurality of layers of graphene sheets dispersed in a liquid phase. In this embodiment, the sandwich 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-layer carbon nanotube film structure holds the graphene sheets in the middle graphene sheet dispersion, thereby making the graphene sheets more firmly fixed. This step is an optional step.

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。In the third step, the carbon nanotube film structure infiltrated by the graphene sheet is dried, so that the graphene sheet and the carbon nanotube film structure are combined to form a graphene sheet-nanocarbon tube film composite structure.

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。After the graphene sheet dispersion is dried, a graphene sheet layer is formed on the surface of the carbon nanotube film structure. The graphene sheets in the graphene sheet layer 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-nanocarbon tube film composite structure, at least one graphene sheet covers at least one micropores in the carbon nanotube film structure.

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。When a three-layer sandwich structure is formed, the carbon nanotubes in the two-layer carbon nanotube film structure sandwich the graphene sheets in the graphene sheet layer, thereby fixing the graphene sheets more stably in the three-layer sandwich layer. In the structure.

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。After forming the graphene sheet-nanocarbon tube film composite structure, the graphene sheet-nano carbon tube film composite structure may be further processed to make the graphene sheet and the carbon nanotube tube in the carbon nanotube film Bonded connection.

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)轟擊該石墨烯片-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。The processing step may specifically be irradiating the graphene sheet-carbon nanotube film composite structure by laser or ultraviolet light; or bombarding the graphene sheet-carbon nanotube film composite structure by high-energy particles. After the treatment, the carbon atoms in the graphene sheet and the carbon atoms in the carbon nanotubes are covalently bonded by sp3 hybridization, so that the graphene sheets are 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.

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。In step four, the graphene sheet-nanocarbon tube film composite structure is covered with a metal grid.

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。The metal mesh has at least one through hole, and the graphene sheet-carbon nanotube film composite structure covers a portion of the through hole.

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。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.

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。Specifically, a laser beam can be used to focus and illuminate between two adjacent metal meshes to blow the graphene sheet-carbon nanotube film composite structure. In this embodiment, the laser beam power is 5 to 30 watts (W), preferably 18 watts.

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,即製成透射電鏡微栅。Further, the graphene sheet-nanocarbon tube film composite structure covering the metal grid may be treated with an organic solvent, so that the graphene sheet-nanocarbon tube film composite structure and the metal grid are tightly combined and along the metal The grid edge removes the excess graphene sheet-nano carbon tube film composite structure, which is made into a transmission electron microstrip.

上述有機溶劑爲常溫下易揮發的有機溶劑,如乙醇、甲醇、丙酮、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,使該石墨烯片-奈米碳管膜複合結構和金屬網格結合緊密。另,可將上述覆蓋有石墨烯片-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。該步驟爲可選擇步驟。The above organic solvent is an organic solvent which is volatile at normal temperature, such as ethanol, methanol, acetone, 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 film composite structure, so that the graphene sheet-nanocarbon tube film composite structure and the metal mesh are tightly combined. Alternatively, the metal mesh covered with the graphene sheet-nanocarbon tube 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. This step is an optional step.

本發明實施例所提供的透射電鏡微栅的製備方法具有以下優點。首先,由於奈米碳管膜及由奈米碳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膜結構上,使兩奈米碳管膜結構夾持其間的石墨烯片。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膜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。The preparation method of the TEM micro-gate provided by the embodiment of the invention has the following advantages. First, since the carbon nanotube film and the carbon nanotube film structure formed by the carbon nanotube film are self-supporting, they can be conveniently laid and laminated, and a carbon nanotube film structure can be conveniently covered. On the other surface of the carbon nanotube film structure having a graphene sheet, the two carbon nanotube film structure is sandwiched between the graphene sheets. Secondly, the method of treating the graphene sheet-nanocarbon tube film composite structure by laser, ultraviolet light or high energy particles enables the graphene sheet and the carbon nanotube film to be more firmly bonded by a covalent bond. Again, since the carbon nanotube film structure has a large specific surface area, it has a large viscosity and can adhere well to the metal mesh, and the carbon nanotube film structure and the metal are treated by an organic solvent. The combination of the grid is stronger. 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.

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。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 . .

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。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.

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。該奈米碳管膜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°。Specifically, referring to FIG. 2 and FIG. 3 together, the carbon nanotube film structure 122 includes a plurality of stacked layers of carbon nanotube film. The carbon nanotube film is obtained by drawing from a carbon nanotube array, and comprises a plurality of carbon nanotubes which are oriented substantially in the same direction and arranged 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 the carbon nanotubes in each layer are arranged in a preferred orientation in one direction, the carbon nanotubes in the adjacent two layers of carbon nanotube membranes have an intersection angle α, 0° < α≦ 90°. This embodiment is preferably 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在該奈米碳管膜結構122中定義多個微孔126。該奈米碳管膜結構122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~1微米,優選地,100奈米以下的微孔可達到60%以上。Referring to FIGS. 5 and 7, the carbon nanotube structure 122 includes a plurality of intersecting nanocarbon lines 128 including carbon nanotubes stacked side by side and gathered by van der Waals force. Further, The nanocarbon line 128 includes carbon nanotubes that are connected end to end by van der Waals force and are arranged in a preferred orientation along substantially the same direction. The intersecting nanocarbon line 128 defines a plurality of micropores 126 in the carbon nanotube membrane structure 122. The size of the micropores 126 of the carbon nanotube membrane structure 122 is related to the number of layers of the carbon nanotube membrane. 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 pores 126 in the carbon nanotube membrane structure 122 may have a size of from 1 nm to 1 μm, and preferably, the pores of 100 nm or less may reach 60% or more.

該石墨烯片124包括一層或多層石墨烯,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。該石墨烯片124的尺寸爲2奈米~10微米。優選地,該石墨烯片的尺寸爲2奈米~1微米。本實施例中,該石墨烯片124包括1層~3層石墨烯。The graphene sheet 124 includes one or more layers of graphene having a size greater than the size of the micropores 126 in the carbon nanotube membrane structure 122 and completely covering the microholes 126. The graphene sheet 124 has a size of 2 nm to 10 μm. Preferably, the graphene sheet has a size of from 2 nm to 1 μm. In this embodiment, the graphene sheet 124 includes 1 to 3 layers of graphene.

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,從而使該石墨烯片124穩定的固定於該奈米碳管膜結構122上。Further, the carbon atoms in the graphene sheet 124 and the carbon atoms in the carbon nanotubes can be bonded by sp3 hybridization, thereby stably fixing the graphene sheet 124 to the carbon nanotube film structure 122. .

進一步地,該石墨烯片-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122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122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122上。Further, the graphene sheet-nanocarbon 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 nanotube film structures 122. between. Referring to FIG. 6, the graphene sheet 124 may be disposed between the two carbon nanotube film structures 122 and sandwiched by the nano carbon line 128 in the two carbon nanotube film structure 122, thereby making the graphene sheet 124 Stabilized on the carbon nanotube membrane structure 122.

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110。該金屬網格110的材料爲銅或其他金屬材料。該石墨烯片-奈米碳管膜複合結構120基本覆蓋該金屬網格110,從而使該石墨烯片-奈米碳管膜複合結構120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110相等的面積及形狀,並完全覆蓋該金屬網格110的所有通孔112。另,該金屬網格110的通孔112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10微米~2毫米。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 110 for transmission electron mirrors. The material of the metal mesh 110 is copper or other metal material. The graphene sheet-nanocarbon tube film composite structure 120 substantially covers the metal grid 110, so that the graphene sheet-carbon nanotube film composite structure 120 can be partially suspended by the metal grid 110, this embodiment The graphene sheet-carbon nanotube film composite structure 120 has the same area and shape as the metal grid 110 and completely covers all the through holes 112 of the metal grid 110. In addition, the aperture of the through hole 112 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 through hole 112 of the metal mesh has a diameter of 10 micrometers to 2 millimeters.

可以理解,該透射電鏡微栅100也可採用其他材料(如陶瓷)製成的網格代替該金屬網格110。It can be understood that the TEM microgrid 100 can also replace the metal mesh 110 with a mesh made of other materials such as ceramics.

本實施例透射電鏡微栅100在應用時,待觀察的樣品200被設置於該透射電鏡微栅100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122的微孔126的石墨烯片124表面。該樣品200可爲奈米顆粒,如奈米線、奈米球或奈米管等。該樣品200的尺寸可小於1微米,優選爲10奈米以下。請參閱圖9及圖10,其爲將一奈米金分散液滴加至上述透射電鏡微栅100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。In the embodiment, the TEM micro-gate 100 is applied, and the sample 200 to be observed is disposed on the surface of the TEM micro-gate 100. 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 film structure 122 . The sample 200 can be a nanoparticle such as a nanowire, a nanosphere or a nanotube. The sample 200 may have a size of less than 1 micron, preferably less than 10 nanometers. Please refer to FIG. 9 and FIG. 10 , which are TEM images of different resolutions obtained by adding a nano-gold dispersion droplet to the surface of the TEM micro-gate 100 and drying under a transmission electron microscope. The black particles in the figure are the nano gold particles to be observed.

本發明實施例提供的透射電鏡微栅100具有以下優點。The TEM micro-gate 100 provided by the embodiment of the present invention has the following advantages.

首先,該石墨烯片124起承載樣品200作用,大量樣品200可均勻分布於石墨烯片124表面,可用於測量樣品200粒徑的統計分布,以及觀察該大量樣品200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膜結構122的微孔126上方,從而提高了該透射電鏡微栅100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。First, the graphene sheet 124 functions as a carrier sample 200, and a large amount of the sample 200 can be uniformly distributed on the surface of the graphene sheet 124, which can be used to measure the statistical distribution of the particle size of the sample 200, and observe the self of the sample 200 on the surface of the graphene sheet. Assembly characteristics. Since the graphene sheet 124 covers the micropores 126, the sample 200 can be carried by the graphene sheet 124 to be evenly distributed over the micropores 126 of the carbon nanotube membrane structure 122, thereby improving the transmission electron microstrip. The probability of carrying 100 pairs of samples. Moreover, the particle diameter of the sample to be tested 200 is not limited, for example, only slightly smaller than the micropores 126.

其次,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具有奈米級微孔126(尺寸在1奈米以上,且小於1微米),故該石墨烯片124的尺寸無須太大,也可完全覆蓋該微孔126,從而使該微栅100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。Secondly, it is difficult to prepare a large-sized graphene sheet 124. The size of the graphene sheet 124 prepared by the prior method is less than 10 μm, and therefore, since the carbon nanotube film structure 122 has nano-scale micropores 126 (the size is 1 nm or more, and less than 1 micrometer), the size of the graphene sheet 124 does not need to be too large, and the micropores 126 can be completely covered, so that the effective area of the microgrid 100 for observation can be maximized, thereby avoiding The micropores are too large, causing the graphene sheets 124 to not completely cover the micropores.

第三,該石墨烯片具有極薄的厚度,單層石墨烯的厚度約0.335奈米,在透射電鏡觀察中産生的襯度噪聲較小,從而可獲得分辨率更高的透射電鏡照片。另,具有小直徑(如2微米以下)通孔的金屬網格必須通過光刻或其它複雜且高成本工藝製備。而本實施例中,該金屬網格110的孔徑無需很小,因此該金屬網格110的成本大大降低。Third, the graphene sheet has an extremely thin thickness, and the thickness of the single-layer graphene is about 0.335 nm, and the contrast noise generated in the transmission electron microscope observation is small, so that a higher resolution TEM image can be obtained. In addition, metal grids with small diameter (eg, less than 2 microns) vias must be fabricated by photolithography or other complex and costly processes. In this embodiment, the aperture of the metal mesh 110 does not need to be small, so the cost of the metal grid 110 is greatly reduced.

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,無需通過熱處理去除雜質。該拉取製備奈米碳管膜的方法簡單,有利於降低該透射電鏡微栅10的成本。本實施例透射電鏡微栅10對承載於其上的待觀測樣品的形貌和結構分析等干擾小,對奈米顆粒樣品的高分辨像影響很小。Fourth, since the carbon nanotube film obtained for drawing from the carbon nanotube array has high purity, it is not necessary to remove impurities by heat treatment. The method for preparing the carbon nanotube film is simple, and is advantageous for reducing the cost of the TEM microgrid 10. In the present embodiment, the transmission electron microstrip microgrid 10 has little interference to the morphology and structural analysis of the sample to be observed carried thereon, and has little influence on the high resolution image of the nanoparticle sample.

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122與石墨烯片124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。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 122 has good matching with the graphene sheet 124. The sp3 covalent bond can be formed by treatment to form a unitary structure, which is convenient for use or long-term storage.

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。此種結構可使該透射電鏡微栅100具有更穩定的結構,便於重複使用或長時間保存。In addition, the graphene sheet-nanocarbon tube film composite structure 120 may include at least two carbon nanotube film structures 122 and sandwich the graphite disposed between the two graphene sheet-carbon nanotube film composite structures 120. Alkene sheet 124. Such a structure allows the TEM microgrid 100 to have a more stable structure for re-use or long-term storage.

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內一點到另一點的最大直線距離。It will 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 to another point. The maximum linear distance, the size of the micro-hole refers to the maximum linear distance from one point to another point in the micro-hole.

綜上所述,本發明確已符合發明專利之要件,遂依法提出專利申請。惟,以上所述者僅為本發明之較佳實施例,自不能以此限制本案之申請專利範圍。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內。In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application 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.

100‧‧‧透射電鏡微柵
112‧‧‧通孔
110‧‧‧金屬網格
120‧‧‧石墨烯片-奈米碳管膜複合結構
122‧‧‧奈米碳管膜結構
124‧‧‧石墨烯片
126‧‧‧微孔
128‧‧‧奈米碳管線
200‧‧‧樣品
100‧‧‧ Transmission electron microscopy
112‧‧‧through hole
110‧‧‧Metal grid
120‧‧‧graphene sheet-nano carbon tube membrane composite structure
122‧‧‧Nano Carbon Membrane Structure
124‧‧‧graphene tablets
126‧‧‧Micropores
128‧‧‧Nano carbon pipeline
200‧‧‧ samples

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。1 is a schematic flow chart of a method for preparing a transmission electron microstrip micro-gate according to an embodiment of the present invention.

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電鏡照片。2 is a scanning electron micrograph of a carbon nanotube film in a transmission electron microstrip micro-gate according to an embodiment of the present invention.

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管膜形成的奈米碳管膜結構的掃描電鏡照片。3 is a scanning electron micrograph of a structure of a carbon nanotube film formed by a plurality of intersecting carbon nanotube films in a transmission electron microscope micro-gate according to an embodiment of the present invention.

圖4爲本發明實施例透射電鏡微栅的結構示意圖。4 is a schematic structural view of a transmission electron microscope micro-gate according to an embodiment of the present invention.

圖5爲本發明實施例透射電鏡微栅中一種石墨烯片-奈米碳管膜結構的結構示意圖。FIG. 5 is a schematic structural view showing a structure of a graphene sheet-nanocarbon tube film in a transmission electron microscope micro-gate according to an embodiment of the present invention.

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。6 is a schematic view showing the structure of another graphene sheet-nanocarbon tube membrane structure in a transmission electron microscope micro-gate according to an embodiment of the present invention.

圖7爲本發明實施例透射電鏡微栅中一種石墨烯片-奈米碳管膜結構的透射電鏡照片。7 is a transmission electron micrograph of a graphene sheet-nanocarbon tube membrane structure in a transmission electron microscope micro-gate according to an embodiment of the present invention.

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。FIG. 8 is a schematic structural view of a TEM micro-gate having a sample on the surface according to an embodiment of the present invention.

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。Fig. 9 is a transmission electron micrograph of a nano-particle for observation of a transmission electron microstrip micro-gate according to an embodiment of the present invention.

圖10爲圖9中應用本發明實施例透射電鏡微栅觀察奈米金顆粒的高分辨率透射電鏡照片。Figure 10 is a high resolution transmission electron micrograph of the nano gold particles observed in the TEM of the embodiment of the present invention.

Claims (23)

一種透射電鏡微栅,其包括一網格,其改進在於:進一步包括一石墨烯片-奈米碳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烯片,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。A TEM micro-gate comprising a grid, the improvement comprising: further comprising a graphene sheet-nanocarbon tube film composite structure covering the grid, and being suspended by the grid portion, the graphene sheet-nai The carbon nanotube film composite structure comprises at least one carbon nanotube film structure and a plurality of graphene sheets, wherein the carbon nanotube film structure comprises a plurality of micropores, wherein at least one micropores are covered by a graphene sheet. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該石墨烯片的尺寸爲2奈米~10微米。The TEM micro-gate according to claim 1, wherein the graphene sheet has a size of 2 nm to 10 μm. 如申請專利範圍第2項所述的透射電鏡微栅,其中,該石墨烯片的尺寸爲2奈米~1微米。The TEM micro-gate according to claim 2, wherein the graphene sheet has a size of 2 nm to 1 μm. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該石墨烯片包括1層~3層石墨烯。The TEM micro-gate according to claim 1, wherein the graphene sheet comprises 1 to 3 layers of graphene. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該奈米碳管膜結構包括多個通過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。The TEM micro-gate according to claim 1, wherein the carbon nanotube film structure comprises a plurality of carbon nanotubes arranged in a preferred orientation along substantially the same direction and connected end to end by a van der Waals force. 如申請專利範圍第5項所述的透射電鏡微栅,其中,該奈米碳管膜結構包括多層奈米碳管膜交叉層叠設置。The TEM micro-gate of claim 5, wherein the carbon nanotube film structure comprises a multi-layered carbon nanotube film cross-stacked arrangement. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該微孔的尺寸爲1奈米~1微米。The TEM microgrid according to claim 1, wherein the micropore has a size of 1 nm to 1 μm. 如申請專利範圍第7項所述的透射電鏡微栅,其中,所述尺寸小於100奈米的微孔占總微孔數量的60%以上。The TEM microgrid according to claim 7, wherein the micropores having a size of less than 100 nm account for more than 60% of the total number of micropores. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該石墨烯片中的碳原子與該奈米碳管膜結構中的碳原子通過sp3雜化鍵合。The TEM microgrid according to claim 1, wherein the carbon atoms in the graphene sheet are bonded to the carbon atoms in the carbon nanotube film structure by sp3 hybridization. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該石墨烯片-奈米碳管膜複合結構包括多個奈米碳管膜結構層叠設置及多個石墨烯片設置於相鄰兩奈米碳管膜結構之間,並通過該相鄰的兩奈米碳管膜結構夾持。The TEM micro-gate according to claim 1, wherein the graphene sheet-nanocarbon tube film composite structure comprises a plurality of carbon nanotube film structure stacked and a plurality of graphene sheets are disposed adjacent to each other The two carbon nanotube membrane structures are sandwiched between the adjacent two carbon nanotube membrane structures. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該網格具有至少一通孔,該通孔的孔徑爲10微米~2毫米。The TEM micro-gate according to claim 1, wherein the grid has at least one through hole having a pore diameter of 10 μm to 2 mm. 如申請專利範圍第1項所述的透射電鏡微栅,其中,該網格的材料爲金屬或陶瓷。The TEM micro-gate according to claim 1, wherein the material of the mesh is metal or ceramic. 一種透射電鏡微栅,其包括一網格,其改進在於:進一步包括一石墨烯片-奈米碳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烯片,該奈米碳管膜結構包括多個奈米碳管線交叉設置以及由該多個交叉設置的奈米碳管線形成的多個微孔,其中,至少一微孔被一石墨烯片覆蓋。A TEM micro-gate comprising a grid, the improvement comprising: further comprising a graphene sheet-nanocarbon tube film composite structure covering the grid, and being suspended by the grid portion, the graphene sheet-nai The carbon nanotube film composite structure comprises at least one carbon nanotube film structure and a plurality of graphene sheets, wherein the carbon nanotube membrane structure comprises a plurality of nano carbon pipeline crossovers and nano carbon pipelines arranged by the plurality of intersections a plurality of micropores formed, wherein at least one of the micropores is covered by a graphene sheet. 如申請專利範圍第13項所述的透射電鏡微栅,其中,該奈米碳管線包括並排且通過凡德瓦爾力聚攏的奈米碳管。The TEM microgrid of claim 13, wherein the nanocarbon pipeline comprises carbon nanotubes stacked side by side and gathered by van der Waals force. 如申請專利範圍第14項所述的透射電鏡微栅,其中,該奈米碳管線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。The TEM microgrid according to claim 14, wherein the nanocarbon pipeline comprises a carbon nanotube arranged end to end by van der Waals force and arranged in a preferred orientation substantially in the same direction. 一種透射電鏡微栅的製備方法,其包括以下步驟:
提供一自支撑的奈米碳管膜結構,以及一石墨烯片分散液,該奈米碳管膜結構包括多個微孔;
將該石墨烯片分散液浸潤該奈米碳管膜結構表面;
乾燥該被石墨烯片浸潤的奈米碳管膜結構,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;以及
將所述石墨烯片-奈米碳管膜複合結構覆蓋一網格。
A method for preparing a transmission electron microstrip, comprising the steps of:
Providing a self-supporting carbon nanotube film structure, and a graphene sheet dispersion comprising a plurality of micropores;
The graphene sheet dispersion is infiltrated into the surface of the carbon nanotube film structure;
Drying the carbon nanotube film structure infiltrated by the graphene sheet, thereby compounding the graphene sheet with the carbon nanotube film structure to form a graphene sheet-nanocarbon tube film composite structure; and forming the graphite The ene-nano carbon nanotube film composite structure covers a grid.
如申請專利範圍第16項所述的透射電鏡微栅的製備方法,其中,進一步包括使用有機溶劑處理所述至少一奈米碳管膜結構的步驟。The method for preparing a TEM micro-gate according to claim 16, wherein the method further comprises the step of treating the at least one carbon nanotube film structure with an organic solvent. 如申請專利範圍第16項所述的透射電鏡微栅的製備方法,其中,將該石墨烯片分散液浸潤該奈米碳管膜結構表面後,進一步包括將另一奈米碳管膜結構覆蓋於上述奈米碳管膜結構通過所述石墨烯片分散液浸潤的表面,形成一夾心結構的步驟。The method for preparing a TEM micro-grid according to claim 16, wherein the graphene sheet dispersion is further immersed in the surface of the carbon nanotube film structure, and further comprises covering another carbon nanotube film structure. And forming a sandwich structure on the surface of the carbon nanotube film structure infiltrated by the graphene sheet dispersion. 如申請專利範圍第16項所述的透射電鏡微栅的製備方法,其中,乾燥該被石墨烯片浸潤的奈米碳管膜結構後,進一步包括以激光或紫外光照射該石墨烯片-奈米碳管膜複合結構;或以高能粒子轟擊該石墨烯片-奈米碳管膜複合結構,使該石墨烯片與該奈米碳管鍵合連接的步驟。The method for preparing a TEM micro-grid according to claim 16, wherein after drying the carbon nanotube film structure impregnated by the graphene sheet, further comprising irradiating the graphene sheet with laser or ultraviolet light a carbon nanotube film composite structure; or a step of bombarding the graphene sheet-nanocarbon tube film composite structure with high energy particles to bond the graphene sheet to the carbon nanotube. 如申請專利範圍第16項所述的透射電鏡微栅的製備方法,其中,將所述石墨烯片-奈米碳管膜複合結構覆蓋所述網格後,進一步包括使用有機溶劑處理使該石墨烯片-奈米碳管膜複合結構和網格結合緊密的步驟。The method for preparing a TEM micro-gate according to claim 16, wherein the graphene sheet-carbon nanotube film composite structure covers the grid, and further comprises treating the graphite with an organic solvent. The olefin-nano carbon nanotube film composite structure and the mesh are tightly combined. 如申請專利範圍第16項所述的透射電鏡微栅的製備方法,其中,將所述石墨烯片-奈米碳管膜複合結構覆蓋所述網格後,進一步包括沿網格邊沿去除多餘的石墨烯片-奈米碳管膜複合結構的步驟。The method for preparing a TEM micro-grid according to claim 16, wherein the graphene sheet-nanocarbon tube film composite structure covers the grid, and further comprises removing excess along the edge of the grid. Step of graphene sheet-nano carbon tube film composite structure. 如申請專利範圍第16項所述的透射電鏡微栅的製備方法,其中,將所述石墨烯片-奈米碳管膜複合結構覆蓋所述網格的方法進一步包括以下步驟:
提供多個網格間隔排列;
將該石墨烯片-奈米碳管膜複合結構整個覆蓋在該多個網格;以及
從相鄰的兩個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網格。
The method for preparing a TEM micro-gate according to claim 16, wherein the method of covering the grid with the graphene sheet-carbon nanotube film composite structure further comprises the following steps:
Provide multiple grid spacing arrangements;
The graphene sheet-nanocarbon tube film composite structure is entirely covered in the plurality of meshes; and the graphene sheet-nanocarbon tube film composite structure is disconnected from the adjacent two grids, thereby being disposable A plurality of meshes are formed which are covered with a graphene sheet-nanocarbon tube film composite structure.
如申請專利範圍第21或22項所述的透射電鏡微栅的製備方法,其中,所述去除多餘的石墨烯片-奈米碳管膜複合結構或從相鄰的兩個網格之間斷開該石墨烯片-奈米碳管膜複合結構的方法爲以激光束聚焦照射並燒蝕該石墨烯片-奈米碳管膜複合結構。The method for preparing a TEM micro-gate according to claim 21 or 22, wherein the removing the excess graphene sheet-carbon nanotube film composite structure or disconnecting from between two adjacent grids The method of the graphene sheet-nanocarbon tube film composite structure is to focus and irradiate the graphene sheet-carbon nanotube film composite structure with a laser beam.
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