WO2022227230A1 - Preparation method for carbon nanotube probe - Google Patents

Preparation method for carbon nanotube probe Download PDF

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Publication number
WO2022227230A1
WO2022227230A1 PCT/CN2021/098451 CN2021098451W WO2022227230A1 WO 2022227230 A1 WO2022227230 A1 WO 2022227230A1 CN 2021098451 W CN2021098451 W CN 2021098451W WO 2022227230 A1 WO2022227230 A1 WO 2022227230A1
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Prior art keywords
carbon nanotube
probe
ion beam
focused ion
preparing
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PCT/CN2021/098451
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French (fr)
Chinese (zh)
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杨树明
程碧瑶
邓惠文
赵书浩
李少博
王飞
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西安交通大学
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Publication of WO2022227230A1 publication Critical patent/WO2022227230A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
    • G01Q60/38—Probes, their manufacture, or their related instrumentation, e.g. holders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention belongs to the technical field of micro-nano manufacturing and measurement, in particular to a preparation method of a carbon nanotube probe.
  • Complex microstructures with high aspect ratio usually refer to micro-nano structures with a width of micro-nano scale and a depth of micro-nano scale, with vertical sidewalls and narrow gaps.
  • the measurement methods are mainly divided into two categories: non-contact method and contact method.
  • the measurement range of typical non-contact optical measurement technology is limited by the wavelength of light waves, and it is not suitable for measuring complex curved surfaces with large variations in unevenness.
  • the commonly used instrument for contact measurement is a high-precision stylus profiler, and the lateral resolution is related to the tip radius.
  • the contact pressure per unit area of the surface to be measured is very large. If the hardness of the surface to be measured is low, the probe will often scratch the surface to be measured. Therefore, this method It is not suitable for micro-nano surfaces processed by soft metals such as copper and aluminum.
  • the scanning probe microscopy contact measurement method has higher resolution, but the length and diameter of the common probe are relatively small, and the resolution is limited by the radius of curvature of the needle tip.
  • the size of the sample is related to the curvature of the probe The radii are comparable, especially when the depth-to-width ratio of the sample structure is large, the ordinary probe will have a significant broadening effect. It is difficult to meet the measurement requirements of structures with large aspect ratios.
  • Carbon nanotubes are a new type of nanomaterials with special structure and outstanding physical and chemical properties, which have broad application prospects. Combining carbon nanotubes and scanning probe microscope probes can greatly improve the imaging performance of atomic force microscopes.
  • the purpose of the present invention is to overcome the defects and deficiencies existing in the prior art, and to provide a preparation method of a carbon nanotube probe to meet the requirements of stability, reliability and high precision in the measurement of high aspect ratio microstructures.
  • the present invention adopts following technical scheme to realize:
  • a preparation method of carbon nanotube probe comprising the following steps:
  • step 1) is as follows:
  • the catalyst and the probe of the scanning probe microscope are placed in the reactor. After the reduction treatment, water vapor and organic matter are introduced to carry out a continuous reaction at high temperature. Carbon nanotubes grow on the surface of the probe of the scanning probe microscope, and the reaction is completed. Then, a probe with carbon nanotube bundles grown at the tip is obtained.
  • a further improvement of the present invention is that the catalyst type is K/SiO 2 , wherein K is Fe, Co, or Ni.
  • a further improvement of the present invention lies in that the reduction treatment process is to treat for 0.5-1.5h at a temperature of 800°C-1000°C in an atmosphere formed by H 2 or CO gas in a reducing atmosphere.
  • a further improvement of the present invention lies in that the molar ratio of water vapor and organic matter is 2:1 or 3:1, and is introduced under the protection of protective gas N2 or Ar inert gas, and the temperature for continuous reaction is 600°C-900°C;
  • the organics are one or more combinations of methane, toluene, acetylene, ethylene, ethanol or phenol.
  • step 2) is as follows:
  • the probe to be processed is fixed on the sample stage of the focused ion beam dual-beam system, and the working distance between the probe and the focused ion beam is determined by adjusting the position of the sample stage, so that the The ion beam output direction of the focused ion beam dual-beam system is aligned with the excess carbon nanotube bundles except for the vertical part of the tip, and the focused ion beam dual-beam system is activated to remove the excess carbon nanotube bundles.
  • the focused ion beam dual-beam system grows in step 1). Probes with carbon nanotube bundles are processed to obtain probe tips with large aspect ratios.
  • a further improvement of the present invention is that the focused ion beam dual-beam system removes excess carbon nanotube bundles by first roughing and then finishing, and controls the energy of the ion beam and the current of the ion beam during the operation.
  • a further improvement of the present invention is that the ion beam of the focused ion beam dual-beam system adopts a gallium ion beam.
  • a further improvement of the present invention is that the working distance between the probe and the focused ion beam dual-beam system is 10-15 mm.
  • the invention provides a preparation method of a carbon nanotube probe, which can obtain a probe of a scanning probe microscope with a large aspect ratio, and has a high-precision measurement capability for the measurement of a complex microstructure with a high aspect ratio.
  • the present invention overcomes the problem that the current probe of the scanning probe microscope is easy to produce imaging artifacts for imaging high aspect ratio fine structures.
  • the preparation method is suitable for probes of various types of scanning probe microscopes. Through the dual beam system of focused ion beam, that is, with scanning electron microscope (SEM) high-magnification electron microscope, processing can be observed in real time, and the carbon nanotube probe can be observed in real time. Controlled preparation.
  • FIG. 1 is a scanning electron microscope picture of the atomic force microscope probe used in the specific embodiment of the present invention.
  • FIG. 2 is a scanning electron microscope picture of carbon nanotube bundles grown on the tip of an atomic force microscope probe in a specific embodiment of the present invention.
  • FIG. 3 is a schematic diagram of a large aspect ratio carbon nanotube probe prepared in a specific embodiment of the present invention.
  • the present invention provides a method for preparing a carbon nanotube probe with a large aspect ratio for measuring a complex microstructure with a high aspect ratio.
  • the specific steps are as follows:
  • the catalyst and the probe of the scanning probe microscope were placed in the reactor and treated for 0.5-1.5 h in a reducing atmosphere formed by H2 or CO gas at a temperature of 800°C-1000°C.
  • a reducing atmosphere formed by H2 or CO gas at a temperature of 800°C-1000°C.
  • protective gas N2 or Ar and other inert gases water vapor and one or more organic substances of methane, toluene, acetylene, ethylene, ethanol or phenol are introduced, and the molar ratio of water vapor to organic substances is 2 : 1 or 3: 1, the continuous reaction temperature is 600°C-900°C, carbon nanotubes grow on the surface of the probe of the scanning probe microscope, and after the reaction is completed, a probe with carbon nanotube bundles growing at the tip is obtained.
  • the focused ion beam system to perform rough processing first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to be 10-15mm (working distance).
  • Distance the distance from the exit end of the ion beam to the sample surface), so that the exit direction of the ion beam of the focused ion beam dual-beam system is aligned with the excess carbon nanotube beam except for the vertical part of the tip, and the energy of the ion beam is set to 30KeV, and the ion beam current is 200-300pA, start the double beam of the focused ion beam system to remove the excess carbon nanotube bundles. After finishing, the energy of the ion beam is set to 20KeV, the current of the ion beam is 100-150pA, and the double beam of the focused ion beam system is activated to remove the excess carbon nanotube bundles.
  • Ni/ SiO2 catalyst and the probe of the atomic force microscope as shown in Fig. 1 were placed in the reactor and treated for 0.5 h under the atmosphere formed by H2 gas in a reducing atmosphere at a temperature of 800 °C. After the reduction treatment, water vapor and methane were introduced under the protection of protective gas N2 , the molar ratio of water vapor to methane was 2:1, and the temperature for the continuous reaction was 600 °C. Carbon nanotubes are grown on the surface of the probe of the atomic force microscope, and after the reaction is completed, the probe with carbon nanotube bundles grown at the tip is shown in Figure 2.
  • the focused ion beam system to perform rough processing first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to 10mm (working distance: The distance from the ion beam exit end to the sample surface), align the ion beam exit direction of the focused ion beam dual-beam system with the excess carbon nanotube beam except for the vertical part of the tip, set the ion beam energy to 30KeV, and the ion beam current to 200pA, The double beam of the focused ion beam system was activated to remove excess carbon nanotube bundles.
  • FIG. 4 is the performance test of the carbon nanotube probe prepared by the present invention
  • Figure 4a is the AFM image of the grating structure measured by the ordinary silicon probe
  • Figure 4b is the AFM image of the grating structure measured by the carbon nanotube probe prepared by the present invention.
  • the Fe/ SiO2 catalyst and the probe of the atomic force microscope as shown in Fig. 1 were placed in the reactor, and treated for 1 h in a reducing atmosphere formed by H2 gas at a temperature of 900 °C. After the reduction treatment, water vapor and methane were introduced under the protection of protective gas N2 , the molar ratio of water vapor to methane was 2:1, and the temperature for the continuous reaction was 600 °C. Carbon nanotubes are grown on the surface of the probe of the atomic force microscope, and after the reaction is completed, the probe with carbon nanotube bundles grown at the tip is shown in Figure 2.
  • the focused ion beam system to perform rough machining first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to be 12mm (working distance: The distance from the exit end of the ion beam to the surface of the sample), align the exit direction of the ion beam of the focused ion beam dual-beam system with the excess carbon nanotube beam except for the vertical part of the tip, set the energy of the ion beam to 30KeV, and set the ion beam current to 250pA.
  • the double beam of the focused ion beam system was activated to remove excess carbon nanotube bundles.
  • the processing process and results can be observed in real time, and then the finishing process is carried out.
  • the energy of the ion beam is set to 20KeV, and the ion beam current is 120pA.
  • the carbon nanotube bundles are removed, and the SEM image of the obtained large aspect ratio carbon nanotube probe is shown in Figure 3.
  • the Co/SiO 2 catalyst and the probe of the electrostatic force microscope were placed in the reactor and treated for 1.5 h in an atmosphere formed by a reducing atmosphere CO gas at a temperature of 1000 °C.
  • a reducing atmosphere CO gas at a temperature of 1000 °C.
  • water vapor and acetylene were introduced under the protection of protective gas N2 , and the molar ratio of water vapor to acetylene was 3:1.
  • the temperature at which the reaction was continued was 900°C.
  • Carbon nanotubes are grown on the surface of the probe of the electrostatic force microscope, and after the reaction is completed, a probe with carbon nanotube bundles growing at the tip is obtained.
  • the focused ion beam system to perform rough processing first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to be 10-15mm (working distance).
  • Distance the distance from the exit end of the ion beam to the sample surface), so that the exit direction of the ion beam of the focused ion beam dual-beam system is aligned with the excess carbon nanotube beam except for the vertical part of the tip, and the energy of the ion beam is set to 30KeV, and the ion beam current is 300pA, start the double beam of the focused ion beam system to remove the excess carbon nanotube bundles.
  • the processing process and results can be observed in real time, and then finishing is performed.
  • the energy of the ion beam is set to 20KeV, and the ion beam current is 150pA.
  • the carbon nanotube bundles are removed to obtain large aspect ratio carbon nanotube probes.

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Abstract

Disclosed is a preparation method for a carbon nanotube probe, comprising the steps of: 1) growing a carbon nanotube bundle at the tip of a scanning probe microscope probe; and 2) using a focused ion beam system to process the probe on which the carbon nanotube bundle is grown so as to obtain an elongated carbon nanotube tip. In the present invention, a scanning probe microscope probe which has a relatively large length-to-diameter ratio may be obtained, and has high-precision measurement capabilities for the measurement of a complex microstructure which has a high depth-to-width ratio.

Description

一种碳纳米管探针的制备方法A kind of preparation method of carbon nanotube probe 技术领域technical field
本发明属于微纳米制造测量技术领域，具体涉及一种碳纳米管探针的制备方法。The invention belongs to the technical field of micro-nano manufacturing and measurement, in particular to a preparation method of a carbon nanotube probe.
背景技术Background technique
随着航空航天，集成电路，微纳传感等应用领域的不断发展，高深宽比复杂微细结构的测量需求不断增加。高深宽比复杂微细结构通常指宽度为微纳米尺度，深度为微米尺度的微纳结构，具有垂直侧壁和狭小间隙的特征。在深度方向上，很难进行精确的测量，且测量是用来保证加工的，其精度往往至少要高于加工一个数量级，所以，如果没有先进的测量手段去保证或检验加工出的三维微结构，就会使其加工无标准可遵循，难以对其结构的功能、用途、新型制造工艺开展更深入的研究。With the continuous development of application fields such as aerospace, integrated circuits, and micro-nano sensing, the measurement requirements for complex microstructures with high aspect ratios continue to increase. Complex microstructures with high aspect ratio usually refer to micro-nano structures with a width of micro-nano scale and a depth of micro-nano scale, with vertical sidewalls and narrow gaps. In the depth direction, it is difficult to perform accurate measurement, and measurement is used to ensure processing, and its accuracy is often at least an order of magnitude higher than that of processing. Therefore, if there is no advanced measurement method to ensure or inspect the processed 3D microstructure , it will make it have no standard to follow, and it is difficult to carry out more in-depth research on the function, use and new manufacturing process of its structure.
目前测量方法主要分为非接触法和接触法两大类。典型的非接触光学测量技术测量范围受到光波波长的限制，不适合测量凹凸变化大的复杂曲面。接触式测量常用的仪器为高精度探针式轮廓仪，横向分辨率与针尖半径有关。测量时由于探针要在一定压力下接触被测表面，这样被测表面单位面积上承受的接触压力很大，如果被测表面硬度较低，探针往往会划伤被测表面，因此该方法不适用于铜、铝等软质金属加工出的微纳表面。此外，目前所用探针大部分是金属钨材质或金刚石制成的，尚无可靠工艺使探针的长径比足够大，对高深宽比微细结构的测量无能为力。相比之下，扫描探针显微术接触测量方法具有较高的分辨率，但普通探针长径比较小，分辨率受限于针尖的曲率半径，当样品的尺寸大小与探针的曲率半径相当，特别是样品结构深宽比较大时，普通探针会产生显著的加宽效应。难以满足大深宽比结构的测量需求。At present, the measurement methods are mainly divided into two categories: non-contact method and contact method. The measurement range of typical non-contact optical measurement technology is limited by the wavelength of light waves, and it is not suitable for measuring complex curved surfaces with large variations in unevenness. The commonly used instrument for contact measurement is a high-precision stylus profiler, and the lateral resolution is related to the tip radius. During measurement, since the probe needs to contact the surface to be measured under a certain pressure, the contact pressure per unit area of the surface to be measured is very large. If the hardness of the surface to be measured is low, the probe will often scratch the surface to be measured. Therefore, this method It is not suitable for micro-nano surfaces processed by soft metals such as copper and aluminum. In addition, most of the probes currently used are made of metal tungsten material or diamond, and there is no reliable process to make the aspect ratio of the probe sufficiently large, and it is powerless to measure the microstructure with high aspect ratio. In contrast, the scanning probe microscopy contact measurement method has higher resolution, but the length and diameter of the common probe are relatively small, and the resolution is limited by the radius of curvature of the needle tip. When the size of the sample is related to the curvature of the probe The radii are comparable, especially when the depth-to-width ratio of the sample structure is large, the ordinary probe will have a significant broadening effect. It is difficult to meet the measurement requirements of structures with large aspect ratios.
碳纳米管是一种具有特殊结构和突出物理化学性能的新型纳米材料，具有广泛的应用前景。将碳纳米管和扫描探针显微镜的探针结合起来，可以极大提高原子力显微镜的成像性能。Carbon nanotubes are a new type of nanomaterials with special structure and outstanding physical and chemical properties, which have broad application prospects. Combining carbon nanotubes and scanning probe microscope probes can greatly improve the imaging performance of atomic force microscopes.
技术问题technical problem
本发明的目的是克服现有技术中存在的缺陷和不足，提供一种碳纳米管探针的制备方法，以满足高深宽比微细结构测量的稳定可靠、精度高等要求。The purpose of the present invention is to overcome the defects and deficiencies existing in the prior art, and to provide a preparation method of a carbon nanotube probe to meet the requirements of stability, reliability and high precision in the measurement of high aspect ratio microstructures.
技术解决方案technical solutions
本发明采用如下技术方案来实现：The present invention adopts following technical scheme to realize:
一种碳纳米管探针的制备方法，包括以下步骤：A preparation method of carbon nanotube probe, comprising the following steps:
1）在扫描探针显微镜探针的尖端生长碳纳米管束；1) Growth of carbon nanotube bundles at the tip of the scanning probe microscope probe;
2）利用聚焦离子束系统对生长有碳纳米管束的探针进行加工得到细长的碳纳米管尖端。2) Using a focused ion beam system to process the probe with carbon nanotube bundles grown thereon to obtain elongated carbon nanotube tips.
本发明进一步的改进在于，步骤1）的具体实现方法如下：A further improvement of the present invention is that the specific implementation method of step 1) is as follows:
将催化剂与扫描探针显微镜的探针置于反应器中，待还原处理后，通入水蒸气和有机物，在高温下进行持续反应，碳纳米管在扫描探针显微镜的探针表面生长，反应完毕后即得尖端生长有碳纳米管束的探针。The catalyst and the probe of the scanning probe microscope are placed in the reactor. After the reduction treatment, water vapor and organic matter are introduced to carry out a continuous reaction at high temperature. Carbon nanotubes grow on the surface of the probe of the scanning probe microscope, and the reaction is completed. Then, a probe with carbon nanotube bundles grown at the tip is obtained.
本发明进一步的改进在于，催化剂类型为K/SiO 2，其中K为Fe、Co、或Ni。 A further improvement of the present invention is that the catalyst type is K/SiO 2 , wherein K is Fe, Co, or Ni.
本发明进一步的改进在于，还原处理过程为在还原性气氛由H 2或CO气体形成的气氛下，温度为800℃-1000℃，处理0.5-1.5h。 A further improvement of the present invention lies in that the reduction treatment process is to treat for 0.5-1.5h at a temperature of 800°C-1000°C in an atmosphere formed by H 2 or CO gas in a reducing atmosphere.
本发明进一步的改进在于，水蒸气和有机物的摩尔比为2：1或3：1，并在保护气体N 2或Ar惰性气体的保护下通入，持续反应的温度为600℃-900℃； A further improvement of the present invention lies in that the molar ratio of water vapor and organic matter is 2:1 or 3:1, and is introduced under the protection of protective gas N2 or Ar inert gas, and the temperature for continuous reaction is 600°C-900°C;
有机物为甲烷、甲苯、乙炔、乙烯、乙醇或苯酚的一种或多种的组合。The organics are one or more combinations of methane, toluene, acetylene, ethylene, ethanol or phenol.
本发明进一步的改进在于，步骤2）的具体实现方法如下：A further improvement of the present invention is that the specific implementation method of step 2) is as follows:
利用聚焦离子束系统，设定加工参数后，将待处理的探针固定在聚焦离子束双束系统的样品台上，通过调节样品台的位置，确定探针与聚焦离子束的工作距离，使聚焦离子束双束系统的离子束出射方向对准除尖端垂直部分的多余碳纳米管束，启动聚焦离子束系统双束对多余碳纳米管束进行去除，聚焦离子束双束系统对步骤1）中生长有碳纳米管束的探针进行加工得到大长径比的探针尖端。Using the focused ion beam system, after setting the processing parameters, the probe to be processed is fixed on the sample stage of the focused ion beam dual-beam system, and the working distance between the probe and the focused ion beam is determined by adjusting the position of the sample stage, so that the The ion beam output direction of the focused ion beam dual-beam system is aligned with the excess carbon nanotube bundles except for the vertical part of the tip, and the focused ion beam dual-beam system is activated to remove the excess carbon nanotube bundles. The focused ion beam dual-beam system grows in step 1). Probes with carbon nanotube bundles are processed to obtain probe tips with large aspect ratios.
本发明进一步的改进在于，聚焦离子束双束系统先采用粗加工，再进行精加工的方式对多余碳纳米管束进行去除，操作中控制离子束的能量与离子束的电流。A further improvement of the present invention is that the focused ion beam dual-beam system removes excess carbon nanotube bundles by first roughing and then finishing, and controls the energy of the ion beam and the current of the ion beam during the operation.
本发明进一步的改进在于，聚焦离子束双束系统的离子束采用镓离子束。A further improvement of the present invention is that the ion beam of the focused ion beam dual-beam system adopts a gallium ion beam.
本发明进一步的改进在于，探针与聚焦离子束双束系统的工作距离为10-15mm。A further improvement of the present invention is that the working distance between the probe and the focused ion beam dual-beam system is 10-15 mm.
有益效果beneficial effect
本发明具有如下有益的技术效果：The present invention has following beneficial technical effect:
本发明提供的一种碳纳米管探针的制备方法，该制备方法能够得到长径比较大的扫描探针显微镜的探针，对高深宽比复杂微细结构的测量具有高精度的测量能力。本发明克服了当前使用扫描探针显微镜的探针对高深宽比微细结构成像易产生成像假象的问题。该制备方法适用于各种类型的扫描探针显微镜的探针，通过聚焦离子束的双束系统即配合扫描电镜（SEM）高倍数电子显微镜可以进行加工实时观察，可以实现碳纳米管探针的可控制备。The invention provides a preparation method of a carbon nanotube probe, which can obtain a probe of a scanning probe microscope with a large aspect ratio, and has a high-precision measurement capability for the measurement of a complex microstructure with a high aspect ratio. The present invention overcomes the problem that the current probe of the scanning probe microscope is easy to produce imaging artifacts for imaging high aspect ratio fine structures. The preparation method is suitable for probes of various types of scanning probe microscopes. Through the dual beam system of focused ion beam, that is, with scanning electron microscope (SEM) high-magnification electron microscope, processing can be observed in real time, and the carbon nanotube probe can be observed in real time. Controlled preparation.
附图说明Description of drawings
图1为本发明具体实施例中使用的原子力显微镜探针扫描电子显微镜图片。FIG. 1 is a scanning electron microscope picture of the atomic force microscope probe used in the specific embodiment of the present invention.
图2为本发明具体实施例中原子力显微镜探针尖端生长有碳纳米管束的扫描电子显微镜图片。2 is a scanning electron microscope picture of carbon nanotube bundles grown on the tip of an atomic force microscope probe in a specific embodiment of the present invention.
图3为本发明具体实施例中制备得到的大长径比碳纳米管探针示意图。3 is a schematic diagram of a large aspect ratio carbon nanotube probe prepared in a specific embodiment of the present invention.
图4为普通硅探针测量光栅结构的AFM图像a与本发明具体实施例中通过可控制备方法得到的大长径比碳纳米管探针测量光栅结构的AFM图像b的对比。4 is a comparison of the AFM image a of the grating structure measured by an ordinary silicon probe and the AFM image b of the grating structure measured by the large aspect ratio carbon nanotube probe obtained by the controllable preparation method in the specific embodiment of the present invention.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
以下结合附图和实施例对本发明进一步解释说明。The present invention will be further explained below in conjunction with the accompanying drawings and embodiments.
本发明提供的一种用于高深宽比复杂微细结构测量的大长径比碳纳米管探针的制备方法，具体步骤如下：The present invention provides a method for preparing a carbon nanotube probe with a large aspect ratio for measuring a complex microstructure with a high aspect ratio. The specific steps are as follows:
1）在扫描探针显微镜探针的尖端生长碳纳米管束1) Growth of carbon nanotube bundles at the tip of a scanning probe microscope probe
将催化剂与扫描探针显微镜的探针置于反应器中，在还原性气氛由H 2或CO气体形成的气氛下处理0.5-1.5h，温度为800℃-1000℃。待还原处理后，在保护气体N 2或Ar等惰性气体的保护下通入水蒸气和甲烷、甲苯、乙炔、乙烯、乙醇或苯酚的一种或多种有机物，水蒸气与有机物的摩尔比为2：1或3：1，持续反应的温度为600℃-900℃，碳纳米管在扫描探针显微镜的探针表面生长，反应完毕后即得尖端生长有碳纳米管束的探针。 The catalyst and the probe of the scanning probe microscope were placed in the reactor and treated for 0.5-1.5 h in a reducing atmosphere formed by H2 or CO gas at a temperature of 800°C-1000°C. After the reduction treatment, under the protection of protective gas N2 or Ar and other inert gases, water vapor and one or more organic substances of methane, toluene, acetylene, ethylene, ethanol or phenol are introduced, and the molar ratio of water vapor to organic substances is 2 : 1 or 3: 1, the continuous reaction temperature is 600°C-900°C, carbon nanotubes grow on the surface of the probe of the scanning probe microscope, and after the reaction is completed, a probe with carbon nanotube bundles growing at the tip is obtained.
2）聚焦离子束加工2) Focused ion beam processing
利用聚焦离子束系统先进行粗加工，将待处理的探针固定在聚焦离子束双束系统的样品台上，调整扫描探针显微镜的探针与聚焦离子束的工作距离为10-15mm（工作距离：离子束出射端到样品表面的距离），使聚焦离子束双束系统的离子束出射方向对准除尖端垂直部分的多余碳纳米管束，设定离子束的能量为30KeV，离子束流为200-300pA，启动聚焦离子束系统双束对多余碳纳米管束进行去除。再进行精加工即设定离子束的能量为20KeV，离子束流为100-150pA，启动聚焦离子束系统双束对多余碳纳米管束进行去除。Use the focused ion beam system to perform rough processing first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to be 10-15mm (working distance). Distance: the distance from the exit end of the ion beam to the sample surface), so that the exit direction of the ion beam of the focused ion beam dual-beam system is aligned with the excess carbon nanotube beam except for the vertical part of the tip, and the energy of the ion beam is set to 30KeV, and the ion beam current is 200-300pA, start the double beam of the focused ion beam system to remove the excess carbon nanotube bundles. After finishing, the energy of the ion beam is set to 20KeV, the current of the ion beam is 100-150pA, and the double beam of the focused ion beam system is activated to remove the excess carbon nanotube bundles.
实施例1Example 1
1）在原子力显微镜探针的尖端生长碳纳米管束1) Growth of carbon nanotube bundles at the tip of an atomic force microscope probe
将Ni/SiO 2催化剂与如图1所示的原子力显微镜的探针置于反应器中，在还原性气氛由H 2气体形成的气氛下处理0.5h，温度为800℃。待还原处理后，在保护气体N 2保护下通入水蒸气和甲烷，水蒸气与甲烷的摩尔比为2：1，持续反应的温度为600℃。碳纳米管在原子力显微镜的探针表面生长，反应完毕后即得尖端生长有碳纳米管束的探针如图2所示。 The Ni/ SiO2 catalyst and the probe of the atomic force microscope as shown in Fig. 1 were placed in the reactor and treated for 0.5 h under the atmosphere formed by H2 gas in a reducing atmosphere at a temperature of 800 °C. After the reduction treatment, water vapor and methane were introduced under the protection of protective gas N2 , the molar ratio of water vapor to methane was 2:1, and the temperature for the continuous reaction was 600 °C. Carbon nanotubes are grown on the surface of the probe of the atomic force microscope, and after the reaction is completed, the probe with carbon nanotube bundles grown at the tip is shown in Figure 2.
2）聚焦离子束加工2) Focused ion beam processing
利用聚焦离子束系统先进行粗加工，将待处理的探针固定在聚焦离子束双束系统的样品台上，调整扫描探针显微镜的探针与聚焦离子束的工作距离为10mm（工作距离：离子束出射端到样品表面的距离），使聚焦离子束双束系统的离子束出射方向对准除尖端垂直部分的多余碳纳米管束，设定离子束的能量为30KeV，离子束流为200pA，启动聚焦离子束系统双束对多余碳纳米管束进行去除。通过配合扫描电镜（SEM）高倍数电子显微镜可以进行加工过程及结果的实时观察，再进行精加工，设定离子束的能量为20KeV，离子束流为100pA，启动聚焦离子束双束系统对多余碳纳米管束进行去除，得到的大长径比碳纳米管探针的SEM图像如图3所示。如图4为本发明制备的碳纳米管探针的性能测试，图4a为普通硅探针测量光栅结构的AFM图像，图4b为本发明制备的碳纳米管探针测量光栅结构的AFM图像。Use the focused ion beam system to perform rough processing first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to 10mm (working distance: The distance from the ion beam exit end to the sample surface), align the ion beam exit direction of the focused ion beam dual-beam system with the excess carbon nanotube beam except for the vertical part of the tip, set the ion beam energy to 30KeV, and the ion beam current to 200pA, The double beam of the focused ion beam system was activated to remove excess carbon nanotube bundles. By cooperating with the scanning electron microscope (SEM) high-magnification electron microscope, the real-time observation of the processing process and the results can be carried out, and then the finishing process is carried out. The carbon nanotube bundles are removed, and the SEM image of the obtained large aspect ratio carbon nanotube probe is shown in Figure 3. Figure 4 is the performance test of the carbon nanotube probe prepared by the present invention, Figure 4a is the AFM image of the grating structure measured by the ordinary silicon probe, and Figure 4b is the AFM image of the grating structure measured by the carbon nanotube probe prepared by the present invention.
1）在原子力显微镜探针的尖端生长碳纳米管束1) Growth of carbon nanotube bundles at the tip of an atomic force microscope probe
将Fe/SiO 2催化剂与如图1所示的原子力显微镜的探针置于反应器中，在还原性气氛由H 2气体形成的气氛下处理1h，温度为900℃。待还原处理后，在保护气体N 2保护下通入水蒸气和甲烷，水蒸气与甲烷的摩尔比为2：1，持续反应的温度为600℃。碳纳米管在原子力显微镜的探针表面生长，反应完毕后即得尖端生长有碳纳米管束的探针如图2所示。 The Fe/ SiO2 catalyst and the probe of the atomic force microscope as shown in Fig. 1 were placed in the reactor, and treated for 1 h in a reducing atmosphere formed by H2 gas at a temperature of 900 °C. After the reduction treatment, water vapor and methane were introduced under the protection of protective gas N2 , the molar ratio of water vapor to methane was 2:1, and the temperature for the continuous reaction was 600 °C. Carbon nanotubes are grown on the surface of the probe of the atomic force microscope, and after the reaction is completed, the probe with carbon nanotube bundles grown at the tip is shown in Figure 2.
2）聚焦离子束加工2) Focused ion beam processing
利用聚焦离子束系统先进行粗加工，将待处理的探针固定在聚焦离子束双束系统的样品台上，调整扫描探针显微镜的探针与聚焦离子束的工作距离为12mm（工作距离：离子束出射端到样品表面的距离），使聚焦离子束双束系统的离子束出射方向对准除尖端垂直部分的多余碳纳米管束，设定离子束的能量为30KeV，离子束流为250pA，启动聚焦离子束系统双束对多余碳纳米管束进行去除。通过配合扫描电镜（SEM）高倍数电子显微镜可以进行加工过程及结果的实时观察，再进行精加工，设定离子束的能量为20KeV，离子束流为120pA，启动聚焦离子束双束系统对多余碳纳米管束进行去除，得到的大长径比碳纳米管探针的SEM图像如图3所示。Use the focused ion beam system to perform rough machining first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to be 12mm (working distance: The distance from the exit end of the ion beam to the surface of the sample), align the exit direction of the ion beam of the focused ion beam dual-beam system with the excess carbon nanotube beam except for the vertical part of the tip, set the energy of the ion beam to 30KeV, and set the ion beam current to 250pA. The double beam of the focused ion beam system was activated to remove excess carbon nanotube bundles. By cooperating with the scanning electron microscope (SEM) high-magnification electron microscope, the processing process and results can be observed in real time, and then the finishing process is carried out. The energy of the ion beam is set to 20KeV, and the ion beam current is 120pA. The carbon nanotube bundles are removed, and the SEM image of the obtained large aspect ratio carbon nanotube probe is shown in Figure 3.
实施例3Example 3
1）在静电力显微镜探针的尖端生长碳纳米管束1) Growth of carbon nanotube bundles at the tip of an electrostatic force microscope probe
将Co/SiO 2催化剂与静电力显微镜的探针置于反应器中，在还原性气氛CO气体形成的气氛下处理1.5h，温度为1000℃。待还原处理后，在保护气体N 2的保护下通入水蒸气和乙炔，水蒸气与乙炔的摩尔比为3：1。持续反应的温度为900℃。碳纳米管在静电力显微镜的探针表面生长，反应完毕后即得尖端生长有碳纳米管束的探针。 The Co/SiO 2 catalyst and the probe of the electrostatic force microscope were placed in the reactor and treated for 1.5 h in an atmosphere formed by a reducing atmosphere CO gas at a temperature of 1000 °C. After the reduction treatment, water vapor and acetylene were introduced under the protection of protective gas N2 , and the molar ratio of water vapor to acetylene was 3:1. The temperature at which the reaction was continued was 900°C. Carbon nanotubes are grown on the surface of the probe of the electrostatic force microscope, and after the reaction is completed, a probe with carbon nanotube bundles growing at the tip is obtained.
2）聚焦离子束加工2) Focused ion beam processing
利用聚焦离子束系统先进行粗加工，将待处理的探针固定在聚焦离子束双束系统的样品台上，调整扫描探针显微镜的探针与聚焦离子束的工作距离为10-15mm（工作距离：离子束出射端到样品表面的距离），使聚焦离子束双束系统的离子束出射方向对准除尖端垂直部分的多余碳纳米管束，设定离子束的能量为30KeV，离子束流为300pA，启动聚焦离子束系统双束对多余碳纳米管束进行去除。通过配合扫描电镜（SEM）高倍数电子显微镜可以进行加工过程及结果的实时观察，再进行精加工，设定离子束的能量为20KeV，离子束流为150pA，启动聚焦离子束双束系统对多余碳纳米管束进行去除，得到的大长径比碳纳米管探针。Use the focused ion beam system to perform rough processing first, fix the probe to be processed on the sample stage of the focused ion beam dual-beam system, and adjust the working distance between the probe of the scanning probe microscope and the focused ion beam to be 10-15mm (working distance). Distance: the distance from the exit end of the ion beam to the sample surface), so that the exit direction of the ion beam of the focused ion beam dual-beam system is aligned with the excess carbon nanotube beam except for the vertical part of the tip, and the energy of the ion beam is set to 30KeV, and the ion beam current is 300pA, start the double beam of the focused ion beam system to remove the excess carbon nanotube bundles. By cooperating with a scanning electron microscope (SEM) high-magnification electron microscope, the processing process and results can be observed in real time, and then finishing is performed. The energy of the ion beam is set to 20KeV, and the ion beam current is 150pA. The carbon nanotube bundles are removed to obtain large aspect ratio carbon nanotube probes.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (9)

  1. 一种碳纳米管探针的制备方法，其特征在于，包括以下步骤：A method for preparing a carbon nanotube probe, comprising the following steps:
    1）在扫描探针显微镜探针的尖端生长碳纳米管束；1) Growth of carbon nanotube bundles at the tip of the scanning probe microscope probe;
    2）利用聚焦离子束系统对生长有碳纳米管束的探针进行加工得到细长的碳纳米管尖端。2) Using a focused ion beam system to process the probe with carbon nanotube bundles grown thereon to obtain elongated carbon nanotube tips.
  2. 根据权利要求1所述的一种碳纳米管探针的制备方法，其特征在于，步骤1）的具体实现方法如下：The method for preparing a carbon nanotube probe according to claim 1, wherein the specific implementation method of step 1) is as follows:
    将催化剂与扫描探针显微镜的探针置于反应器中，待还原处理后，通入水蒸气和有机物，在高温下进行持续反应，碳纳米管在扫描探针显微镜的探针表面生长，反应完毕后即得尖端生长有碳纳米管束的探针。The catalyst and the probe of the scanning probe microscope are placed in the reactor. After the reduction treatment, water vapor and organic matter are introduced to carry out a continuous reaction at high temperature. Carbon nanotubes grow on the surface of the probe of the scanning probe microscope, and the reaction is completed. Then, a probe with carbon nanotube bundles grown at the tip is obtained.
  3. 根据权利要求2所述的一种碳纳米管探针的制备方法，其特征在于，催化剂类型为K/SiO 2，其中K为Fe、Co、或Ni。 The method for preparing a carbon nanotube probe according to claim 2, wherein the catalyst type is K/SiO 2 , wherein K is Fe, Co, or Ni.
  4. 根据权利要求2所述的一种碳纳米管探针的制备方法，其特征在于，还原处理过程为在还原性气氛由H 2或CO气体形成的气氛下，温度为800℃-1000℃，处理0.5-1.5h。 The method for preparing a carbon nanotube probe according to claim 2, characterized in that, the reduction treatment process is in an atmosphere formed by H2 or CO gas in a reducing atmosphere, at a temperature of 800°C-1000°C, and treating 0.5-1.5h.
  5. 根据权利要求2所述的一种碳纳米管探针的制备方法，其特征在于，水蒸气和有机物的摩尔比为2：1或3：1，并在保护气体N 2或Ar惰性气体的保护下通入，持续反应的温度为600℃-900℃； The method for preparing a carbon nanotube probe according to claim 2, characterized in that the molar ratio of water vapor and organic matter is 2:1 or 3:1, and under the protection of protective gas N2 or Ar inert gas The temperature of continuous reaction is 600 ℃-900 ℃;
    有机物为甲烷、甲苯、乙炔、乙烯、乙醇或苯酚的一种或多种的组合。The organics are one or more combinations of methane, toluene, acetylene, ethylene, ethanol or phenol.
  6. 根据权利要求2所述的一种碳纳米管探针的制备方法，其特征在于，步骤2）的具体实现方法如下：The method for preparing a carbon nanotube probe according to claim 2, wherein the specific implementation method of step 2) is as follows:
    利用聚焦离子束系统，设定加工参数后，将待处理的探针固定在聚焦离子束双束系统的样品台上，通过调节样品台的位置，确定探针与聚焦离子束的工作距离，使聚焦离子束双束系统的离子束出射方向对准除尖端垂直部分的多余碳纳米管束，启动聚焦离子束系统双束对多余碳纳米管束进行去除，聚焦离子束双束系统对步骤1）中生长有碳纳米管束的探针进行加工得到大长径比的探针尖端。Using the focused ion beam system, after setting the processing parameters, the probe to be processed is fixed on the sample stage of the focused ion beam dual-beam system, and the working distance between the probe and the focused ion beam is determined by adjusting the position of the sample stage, so that the The ion beam output direction of the focused ion beam dual-beam system is aligned with the excess carbon nanotube bundles except for the vertical part of the tip, and the focused ion beam dual-beam system is activated to remove the excess carbon nanotube bundles. The focused ion beam dual-beam system grows in step 1). Probes with carbon nanotube bundles are processed to obtain probe tips with large aspect ratios.
  7. 根据权利要求6所述的一种碳纳米管探针的制备方法，其特征在于，聚焦离子束双束系统先采用粗加工，再进行精加工的方式对多余碳纳米管束进行去除，操作中控制离子束的能量与离子束的电流。The method for preparing a carbon nanotube probe according to claim 6, wherein the focused ion beam dual-beam system first removes the excess carbon nanotube bundles by roughing and then finishing, and controls the operation during the operation. The energy of the ion beam and the current of the ion beam.
  8. 根据权利要求6所述的一种碳纳米管探针的制备方法，其特征在于，聚焦离子束双束系统的离子束采用镓离子束。The method for preparing a carbon nanotube probe according to claim 6, wherein the ion beam of the focused ion beam dual-beam system adopts a gallium ion beam.
  9. 根据权利要求6所述的一种碳纳米管探针的制备方法，其特征在于，探针与聚焦离子束双束系统的工作距离为10-15mm。The method for preparing a carbon nanotube probe according to claim 6, wherein the working distance between the probe and the focused ion beam dual-beam system is 10-15 mm.
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