WO2016074305A1 - Graphene-coated atomic force microscope probe and manufacturing method therefor and application thereof - Google Patents

Graphene-coated atomic force microscope probe and manufacturing method therefor and application thereof Download PDF

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WO2016074305A1
WO2016074305A1 PCT/CN2014/093684 CN2014093684W WO2016074305A1 WO 2016074305 A1 WO2016074305 A1 WO 2016074305A1 CN 2014093684 W CN2014093684 W CN 2014093684W WO 2016074305 A1 WO2016074305 A1 WO 2016074305A1
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graphene
atomic force
force microscope
probe
coated
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PCT/CN2014/093684
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French (fr)
Chinese (zh)
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惠飞
兰扎马里奥
石媛媛
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苏州大学张家港工业技术研究院
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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
    • G01Q60/40—Conductive probes

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  • the invention belongs to the field of atomic force microscopy, relates to an atomic force microscope probe, a preparation method thereof and a use thereof, in particular to a durable graphene coated atomic force microscope probe, a preparation method thereof and use thereof.
  • Atomic force microscopy is an important instrument for surface topography acquisition and electromagnetic performance analysis with atomic resolution. It is an important characterization tool in the fields of surface science and nanotechnology. Among them, the AFM probe is an important part of the atomic force microscope and belongs to the common consumables of the high-tech equipment. Its main manufacturers are distributed in Germany, Switzerland, the United States, Japan and other countries. Ordinary AFM probes are mainly prepared by processing silicon or silicon nitride by means of MEMS technology, while conductive AFM probes are plated with 10-50 nm thick metal platinum on the surface of common probes (and other metals that improve coating adhesion). Obtained, such as titanium, chromium, platinum and rhodium.
  • conductive AFM probes are prone to wear during their use, which makes it difficult to maintain electrical conductivity for a long time. Therefore, many countries are working on new probes with high resolution and long service life.
  • the new products of conductive AFM tip have carbon nanotube-based tip, diamond coated tip and full wire tip.
  • Graphene which is widely used in various research fields due to its superior single layer thickness, high conductivity, thermal conductivity, high mobility, etc., has also been used by some groups to prepare conductive atomic force microscope probes.
  • the graphene AFM probe was obtained for the first time by directly growing graphene on a gold-plated AFM probe by chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • ethanol is used as a carbon source
  • gold is used as a catalyst
  • a mixed gas of hydrogen and argon is used as a carrier gas.
  • the ethanol was placed in a low temperature zone, and the gold-plated AFM probe was placed in a high temperature zone (750-850 ° C), and a mixture of a flow rate of 100 mL/min under standard conditions was introduced. After 5 minutes, a graphene layer was formed on the gold surface.
  • the method grows graphene on a copper template by filling and etching a SU-8 photoresist and finally obtains a graphene-modified AFM probe.
  • the first step of the method is to selectively etch the silicon wafer with sodium hydroxide to form a hot oxide layer, and then plate copper on the surface as a substrate for graphene deposition; the second step is to obtain continuous on the substrate by chemical vapor deposition.
  • the third step using the SU-8 photoresist to fill the tip mold, performing the exposure and development operation; the fourth step, the dry argon gas is introduced to remove the graphene region without the photoresist on the surface, and simultaneously, spin coating A second layer of SU-8 photoresist is used to form the cantilever of the probe. Finally, excess silicon oxide or the like on the back surface of the needle tip is removed, and the remaining portion is washed to obtain the entire AFM probe.
  • the graphene grown on the copper surface was directly transferred to a conductive AFM probe by a transfer method.
  • a layer of PMMA is spin-coated on the copper-based graphene, and then the copper substrate is etched with a ferric chloride solution, and then washed with hydrochloric acid and an aqueous solution to obtain a PMMA/graphene layer; the conductive AFM probe is used as a substrate for receiving graphene.
  • the transfer it was left to dry for a while (the graphene was attached to the surface of the probe), and then the PMMA was removed with acetone, and finally washed with water to obtain a graphene-covered AFM probe.
  • the copper foil is generally used as the substrate for graphene growth, a higher quality graphene layer can be obtained, but the transfer process of the method is complicated, and the PMMA is not easily removed, thereby reducing The quality of graphene thus affects the performance of the graphene AFM probe.
  • Nanoscale electrical characterization is a necessary step in the analysis of the properties of many materials in scientific and industrial applications.
  • the most effective characterization tool in this field is the conductive atomic force microscope, which is capable of characterizing the electrical properties of conductors and thin insulating materials in a small size range. nature.
  • the conductive atomic force microscope probe is indispensable as an important part of the sample scanning, which consists of three parts: the probe base, the cantilever and the tip.
  • the commonly used conductive AFM probe is a metal coated with a certain thickness (nanoscale) on the surface of the silicon probe, high current and large friction during use can cause the metal plating to wear, which not only leads to unreality.
  • the topographical image, and the rapid consumption of the probe also increases the cost of the study.
  • the invention will greatly reduce the rapid wear of the needle tip and prolong the service life of the probe.
  • commercially available conductive AFM probes have diamond probes that use a stable diamond coating. Although the probe is low in wear, it increases the radius of the probe and reduces its lateral resolution. The present invention will maintain a smaller tip radius of curvature of the tip to maintain the probe with a high resolution.
  • the present invention uses low-cost graphene as a cladding material, which greatly reduces the manufacturing cost.
  • Other conductive AFM probes may cause metal atoms of the plating layer to infiltrate the sample to introduce contamination of the sample.
  • the present invention is incapable of imposing the impermeability of the graphene honeycomb structure and the strong atomic bond energy between the carbon atoms. Move to the sample to avoid contamination of the sample.
  • (5) For chemical vapor deposition, the preparation of high quality graphene is very strong for its growth substrate. Selectivity, while the common AFM tip is not a benign substrate for graphene growth, so a new approach to preparing high quality graphene coated AFM tips is needed.
  • the invention coats the high quality graphene on the AFM needle tip to avoid the adverse effects caused by the poor quality of the graphene.
  • a graphene-coated atomic force microscope probe comprises a probe substrate, a cantilever, a needle tip, a metal layer on the cantilever and the needle tip, and a graphene layer on the needle tip.
  • the metal layer is a bimetal layer, titanium and platinum respectively from the inside to the outside; or the metal layer is a single metal layer, a single metal It is an alloy of platinum and rhodium.
  • the graphene coated atomic force microscope probe has a graphene layer of 1 to 3 layers and a thickness of 0.34-1 nm.
  • the graphene is coated with an atomic force microscope probe, and the probe substrate is silicon or silicon nitride.
  • a method for preparing a graphene-coated atomic force microscope probe comprising the following steps:
  • the graphene prepared by the step (1) in the preparation method of the graphene-coated atomic force microscope probe has an average graphene size of less than 1 micrometer and a thickness of 1-5 layers, and each layer has a thickness of 0.334 nm.
  • the method for preparing a graphene-coated atomic force microscope probe wherein the metal layer is a bimetal layer, and titanium and platinum are respectively from the inside to the outside; or the metal layer is a single metal layer.
  • the single metal is an alloy of platinum and rhodium.
  • Graphene has a large specific surface area and good flexibility and ductility, so that it can be firmly adsorbed on the surface of the probe by means of van der Waals force, so that the tip of the needle can be completely covered by the graphene layer.
  • the invention has the following beneficial effects:
  • the cost of research can be reduced, the life of the probe can be extended, and multiple experiments can be performed to reduce the loss of the probe.
  • the reliability of the test data is increased, and the graphene AFM probe does not contaminate the sample and can provide a real image.
  • the manufacturing cost of the graphene probe is reduced, the preparation method is simple, fast, and the cost is low, and the raw material can be utilized multiple times. Secondly, it is easy to industrialize and apply.
  • the preparation process does not require manpower, and all of them can be automated, and the products can meet the supply and demand.
  • the method for preparing the graphene-coated AFM probe of the invention has obvious advantages compared with the prior art preparation method (CVD method, etching method, transfer method): 1.
  • the technology does not require professional equipment, such as a lithography machine, CVD System, etc.; 2. No harsh conditions, no restrictions on the preparation conditions, such as high temperature, inert atmosphere; 3.
  • the preparation technique is simple, the effect is outstanding, the processing cost is reduced, and the industrialization is easy.
  • Figure 1 is an SEM image of a platinum-titanium atomic force microscope probe without a graphene layer.
  • FIG. 2 is an SEM image of a graphene coated platinum-titanium atomic force microscope probe.
  • Figure 3 is a partial TEM image of a graphene coated platinum-titanium atomic force microscope probe tip.
  • Figure 4 is a current-voltage line taken before and after scanning of a platinum-plated titanium atomic force microscope probe without a graphene layer.
  • Figure 5 is a current-voltage line taken before and after scanning of a graphene-coated platinum-titanium atomic force microscope probe.
  • Fig. 6 is a graph showing the total scan area obtained by a plurality of experiments conducted by a conductive atomic force microscope probe without a graphene layer and a graphene-coated atomic force microscope probe prepared by a different method.
  • Figure 7 is a schematic illustration of a graphene coated atomic force microscope probe of the present invention.
  • the platinum-titanium atomic force microscope probe is an atomic force microscope probe of a bimetal layer of titanium and platinum, respectively, from the inside to the outside.
  • a graphene AFM probe was prepared by a CVD method: ethanol as a carbon source, gold as a catalyst, and a mixed gas of hydrogen and argon as a carrier gas. The ethanol was placed in a low temperature zone, and the gold-plated AFM probe was placed in a high temperature zone (750-850 ° C), and a mixture of a flow rate of 100 mL/min under standard conditions was introduced. After 5 minutes, a graphene layer was formed on the gold surface.
  • Etching-CVD method for preparing graphene AFM probe the first step of the method is to selectively etch silicon wafer with sodium hydroxide to form a hot oxide layer, and then plate copper on the surface as a substrate for graphene deposition; Step, obtaining a continuous graphene layer on the substrate by chemical vapor deposition; in the third step, filling the needle tip mold with SU-8 photoresist, performing exposure development operation; and fourth step, removing dry argon gas to remove the surface The graphene region of the photoresist is simultaneously spin coated with a second layer of SU-8 photoresist to form the cantilever of the probe. Finally, excess silicon oxide or the like on the back surface of the needle tip is removed, and the remaining portion is washed to obtain the entire AFM probe.
  • Preparation of graphene AFM probe by transfer method firstly, a layer of PMMA is spin-coated on copper-based graphene, and then the copper substrate is etched with ferric chloride solution, and then washed with hydrochloric acid and aqueous solution to obtain PMMA/graphene layer; conductive AFM The probe serves as a substrate for receiving graphene. After transfer, it is left to dry for a period of time until the graphene is attached to the surface of the probe. The PMMA is removed by acetone, and finally washed with water to obtain a graphene-covered AFM probe.
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • CAFM conductive atomic force microscopy
  • CAFM characterization copper-based single-layer graphene as a scanning sample, using atomic force microscope probes containing a graphene layer and a bimetal layer of titanium and platinum, respectively, from the inside to the outside, and graphite prepared by the technical means of the present invention
  • the ene coated AFM probe was subjected to an uninterrupted scanning test, and under the same test conditions, multiple scans were performed until the probe lost conductivity.
  • the probe is in ohmic contact with the sample before scanning the sample, and after the end of the scanning, the bimetal layer of titanium and platinum is not contained in the graphene layer from the inside to the outside.
  • a high-order Schottky barrier is formed between the AFM probe and the sample (high degree of tip wear), while the graphene-coated probe has a lower Schottky barrier (lower tip wear), therefore, graphite
  • the olefin greatly reduces the degree of wear of the probe, and this result can also be visually obtained from the SEM image.
  • the experimental results show that the total scan area measured by the graphene-coated AFM probe is the total scan area that can be measured by an atomic force microscope probe with a graphene layer and a bimetal layer of titanium and platinum, respectively. 6-10 times.
  • Figure 6 compares the total scan area statistics obtained by atomic force microscopy probes of graphene-free bimetal layers with titanium and platinum, respectively, and graphene AFM probes prepared by different methods.
  • the results show that the graphene AFM probe prepared by the technique of the present invention has higher electrical conductivity than the graphene AFM probe prepared by other methods and the platinum-titanium atomic force microscope probe without graphene layer and other methods.
  • Graphene probes have the longest lifespan.

Abstract

A graphene-coated atomic force microscope probe and a manufacturing method therefor and an application thereof. The graphene-coated atomic force microscope probe includes a probe base, a cantilever and a tip. The cantilever and the tip are provided with a metal layer, and the tip is further provided with a graphene layer. The manufacturing method for the graphene-coated atomic force microscope probe comprises the following steps: (1) preparing the graphene solution: adding 5-10 mg of graphene into 1mL of water, and performing the ultrasonic dispersion for 10 min in an ultrasonic wave cleaner to obtain 5-10mg/mL of graphene solution; (2) preparing the graphene-coated atomic force microscope probe: immersing the tip of the atomic force microscope probe with the metal layer on the cantilever and the tip, into the graphene solution of step (1), and stirring mechanically for 30-60s, and then extracting the probe to dry naturally.

Description

一种石墨烯包覆原子力显微镜探针及其制备方法、用途Graphene coated atomic force microscope probe, preparation method thereof and use thereof 技术领域Technical field
本发明属于原子力显微镜领域，涉及一种原子力显微镜探针及其制备方法、用途，特别是涉及一种耐用性石墨烯包覆原子力显微镜探针及其制备方法、用途。The invention belongs to the field of atomic force microscopy, relates to an atomic force microscope probe, a preparation method thereof and a use thereof, in particular to a durable graphene coated atomic force microscope probe, a preparation method thereof and use thereof.
背景技术Background technique
原子力显微镜(AFM)是一种具有原子级分辨率的用于表面形貌采集、电磁性能分析的重要仪器，是表面科学、纳米技术等领域的重要表征工具。其中，AFM探针是原子力显微镜中的重要组成部分，属于该高科技设备的常用的耗材，其主要生产厂家分布在德国、瑞士、美国、日本等国家。普通AFM探针主要是通过利用微机电***技术手段加工硅或氮化硅来制备，而导电AFM探针是在普通探针表面镀10-50nm厚的金属铂(及其他提高镀层结合力的金属，如钛、铬，铂和铱等)获得。然而，导电AFM探针在使用过程中其导电镀层易于磨损，导致其导电性难以长期有效保持，所以很多国家的相关机构都在致力于研发具有高分辨率和更长使用寿命的新型探针。目前，导电AFM针尖的新产品有基于碳纳米管的针尖，金刚石镀层针尖和全金属丝针尖等，这些新技术虽然在一定程度上克服了普通导电AFM针尖寿命较短和分辨率不高的缺点，但是其制备过程十分复杂，且生产成本较高。Atomic force microscopy (AFM) is an important instrument for surface topography acquisition and electromagnetic performance analysis with atomic resolution. It is an important characterization tool in the fields of surface science and nanotechnology. Among them, the AFM probe is an important part of the atomic force microscope and belongs to the common consumables of the high-tech equipment. Its main manufacturers are distributed in Germany, Switzerland, the United States, Japan and other countries. Ordinary AFM probes are mainly prepared by processing silicon or silicon nitride by means of MEMS technology, while conductive AFM probes are plated with 10-50 nm thick metal platinum on the surface of common probes (and other metals that improve coating adhesion). Obtained, such as titanium, chromium, platinum and rhodium. However, conductive AFM probes are prone to wear during their use, which makes it difficult to maintain electrical conductivity for a long time. Therefore, many countries are working on new probes with high resolution and long service life. At present, the new products of conductive AFM tip have carbon nanotube-based tip, diamond coated tip and full wire tip. These new technologies overcome the shortcomings of short life and low resolution of common conductive AFM tips. However, the preparation process is very complicated and the production cost is high.
由于具有单原子层厚度，高导电、导热性，高迁移率等优异性质而被广泛应用于各个研究领域的石墨烯也被一些课题组用于制备导电原子力显微镜探针。Graphene, which is widely used in various research fields due to its superior single layer thickness, high conductivity, thermal conductivity, high mobility, etc., has also been used by some groups to prepare conductive atomic force microscope probes.
1.Wen(Y.Wen,J.Chen,Y.Guo,B.Wu,G.Yu and Y.Liu,Multilayer.Graphene-Coated atomic Force Microscopy Tips for Molecular Junctions,Adv.Mater.,2012,24,3482–3485)等通过化学气相沉积法(CVD)直接在镀金AFM探针上生长石墨烯，首次得到石墨烯AFM探针。其中乙醇作为碳源，金作为催化剂，氢气和氩气混合气作为载流气体。乙醇放置在低温区内，镀金AFM探针放置在高温区(750-850℃)，通入在标况下流速为100mL/min的混合气。5分钟后，在金表面形成石墨烯层。1.Wen (Y.Wen, J. Chen, Y. Guo, B. Wu, G. Yu and Y. Liu, Multilayer. Graphene-Coated atomic Force Microscopy Tips for Molecular Junctions, Adv. Mater., 2012, 24, 3482–3485) The graphene AFM probe was obtained for the first time by directly growing graphene on a gold-plated AFM probe by chemical vapor deposition (CVD). Among them, ethanol is used as a carbon source, gold is used as a catalyst, and a mixed gas of hydrogen and argon is used as a carrier gas. The ethanol was placed in a low temperature zone, and the gold-plated AFM probe was placed in a high temperature zone (750-850 ° C), and a mixture of a flow rate of 100 mL/min under standard conditions was introduced. After 5 minutes, a graphene layer was formed on the gold surface.
2.Martin-Olmos(C.Martin-Olmos,H.I.Rasool,B.H.Weiller and J.K.Gimzewski,Graphene MEMS:AFM Probe Performance Improvement,ACS Nano,2013,7(5),4164–4170.)等用刻蚀-CVD法通过填充和刻蚀SU-8光刻胶在铜模板上生长石墨烯并最终得到石墨烯修饰的AFM探针。该方法第一步用氢氧化钠选择性刻蚀硅片，形成热的氧化层，再在其表面镀上铜作为石墨烯沉积的基底；第二步，通过化学气相沉积法在基底上得到连续的石墨烯层；第三步，使用SU-8光刻胶填充针尖模子，进行曝光显影操作；第四步，通入干燥的氩气除去表面没有光刻胶的石墨烯区域，同时，旋涂第二层SU-8光刻胶以形成探针的悬臂。最后，除去针尖背面多余的氧化硅等，清洗剩余部分，从而得到整个AFM探针。 2. Martin-Olmos (C. Martin-Olmos, HI Rasool, BH Weiller and JK Gimzewski, Graphene MEMS: AFM Probe Performance Improvement, ACS Nano, 2013, 7(5), 4164-4170.) The method grows graphene on a copper template by filling and etching a SU-8 photoresist and finally obtains a graphene-modified AFM probe. The first step of the method is to selectively etch the silicon wafer with sodium hydroxide to form a hot oxide layer, and then plate copper on the surface as a substrate for graphene deposition; the second step is to obtain continuous on the substrate by chemical vapor deposition. The graphene layer; the third step, using the SU-8 photoresist to fill the tip mold, performing the exposure and development operation; the fourth step, the dry argon gas is introduced to remove the graphene region without the photoresist on the surface, and simultaneously, spin coating A second layer of SU-8 photoresist is used to form the cantilever of the probe. Finally, excess silicon oxide or the like on the back surface of the needle tip is removed, and the remaining portion is washed to obtain the entire AFM probe.
3.Shim(W.Shim,K.A.Brown,X.Zhou,B.Rasina,X.Liao and C.A.Mirkina,Multifunctional cantilever-free scanning probe arrays coated with multilayer graphene,Proc.Natl.Acad.Sci.U.S.A.,2012,109(45),18312–18317.)和Mario(M.Lanza,A.Bayerl,T.Gao,M.Porti,M.Nafria,G.Jing,Y.Zhang,A.Liu and H.Duan,Graphene-coated Atomic Force Microscope tips for reliable nanoscale electrical characterization,Adv.Mater.,2013,25,1440–1444.)等通过转移法直接将生长在铜表面的石墨烯转移至导电AFM探针上。首先在铜基石墨烯上旋涂一层PMMA，后用三氯化铁溶液刻蚀铜基底，分别用盐酸和水溶液清洗后得到PMMA/石墨烯层；导电AFM探针作为接收石墨烯的基底，转移后晾一段时间至干燥(石墨烯附着在探针表面)后用丙酮除去PMMA，最后用水清洗即可得到石墨烯覆盖的AFM探针。3.Shim (W.Shim, KA Brown, X. Zhou, B. Rasina, X. Liao and CAMirkina, Multifunctional cantilever-free scanning probe arrays coated with multilayer graphene, Proc. Natl. Acad. Sci. USA, 2012, 109(45), 18312–18317.) and Mario (M.Lanza, A. Bayerl, T.Gao, M.Porti, M. Nafria, G.Jing, Y.Zhang, A.Liu and H.Duan, Graphene -coated Atomic Force Microscope tips for reliable nanoscale electrical characterization, Adv. Mater., 2013, 25, 1440 - 1444.) The graphene grown on the copper surface was directly transferred to a conductive AFM probe by a transfer method. First, a layer of PMMA is spin-coated on the copper-based graphene, and then the copper substrate is etched with a ferric chloride solution, and then washed with hydrochloric acid and an aqueous solution to obtain a PMMA/graphene layer; the conductive AFM probe is used as a substrate for receiving graphene. After the transfer, it was left to dry for a while (the graphene was attached to the surface of the probe), and then the PMMA was removed with acetone, and finally washed with water to obtain a graphene-covered AFM probe.
虽然通过这些方法制备得到的石墨烯AFM探针在一定程度上提高了探针的使用性能，但是这些制备方法仍然存在较大的缺陷。对于化学气相沉积法，直接在探针上得到的碳膜其质量远低于在铜箔上生长得到碳膜质量。对于用石墨烯覆盖铜模制得的探针存在两大问题：1.该制备方法需要一项全新的生产加工工艺，成本高且需要专业操作，条件苛刻；2.制得的探针针尖具有较大的曲率半径，影响横向分辨率。而对于转移法得到的石墨烯AFM探针，虽然通常铜箔作为石墨烯生长的基底，可得到较高质量的石墨烯层，但该方法转移过程较为复杂，且PMMA不易除干净，因此会降低石墨烯的质量从而影响石墨烯AFM探针的性能。Although the graphene AFM probe prepared by these methods improves the performance of the probe to a certain extent, these preparation methods still have large defects. For chemical vapor deposition, the mass of the carbon film obtained directly on the probe is much lower than that of the carbon film grown on the copper foil. There are two major problems with the probes made of graphene-coated copper: 1. The preparation method requires a completely new production process, which is costly and requires professional operation and harsh conditions; 2. The prepared probe tip has Larger radius of curvature affects lateral resolution. For the graphene AFM probe obtained by the transfer method, although the copper foil is generally used as the substrate for graphene growth, a higher quality graphene layer can be obtained, but the transfer process of the method is complicated, and the PMMA is not easily removed, thereby reducing The quality of graphene thus affects the performance of the graphene AFM probe.
发明内容Summary of the invention
纳米尺度的电学表征是科研和工业应用中分析许多材料性能的必要步骤，在这个领域中，最有效的表征工具是导电原子力显微镜，它能够在小尺寸范围内表征导体和薄绝缘层材料的电学性质。其中，导电原子力显微镜探针作为样品扫描的重要组成部分是不可或缺的，其由探针基底，悬臂，针尖三部分组成。本发明的目的包括以下几个方面：Nanoscale electrical characterization is a necessary step in the analysis of the properties of many materials in scientific and industrial applications. The most effective characterization tool in this field is the conductive atomic force microscope, which is capable of characterizing the electrical properties of conductors and thin insulating materials in a small size range. nature. Among them, the conductive atomic force microscope probe is indispensable as an important part of the sample scanning, which consists of three parts: the probe base, the cantilever and the tip. The objects of the present invention include the following aspects:
(1)由于通常使用的普通导电AFM探针是在硅探针表面镀一定厚度(纳米级)的金属，而在使用过程中高电流和大的摩擦力会使金属镀层磨损，不仅导致得到不真实的形貌图像，而且探针的快速消耗也增加了研究的成本。本发明将大幅降低针尖的快速磨损，延长探针的使用寿命。(2)目前，市售的导电AFM探针有金刚石探针，使用稳定的金刚石镀层，虽然保证了探针的低磨损度，但是增加了探针的半径，降低了其横向分辨率。本发明将保持针尖较小的针尖曲率半径以保持探针具有高分辨率。(3)其他的固体金属或金刚石镀层大大提高了探针的***格，本发明采用成本低廉的石墨烯作为包覆层材料，大幅降低制造成本。(4)其他导电AFM探针会造成镀层的金属原子渗入样品而引入对样品的污染，本发明由于石墨烯蜂窝状结构的不可渗透性和碳原子之间强的原子键能，使得金属原子不能向样品迁移，避免样品的污染。(5)对于化学气相沉积法由于高质量石墨烯的制备对其生长基底具有很强的 选择性，而普通AFM针尖并不是石墨烯生长的良性基底，所以需探索制备高质量石墨烯包覆的AFM针尖的新方法。本发明将高质量石墨烯包覆在AFM针尖上，避免石墨烯质量较差而导致的不良影响。(1) Since the commonly used conductive AFM probe is a metal coated with a certain thickness (nanoscale) on the surface of the silicon probe, high current and large friction during use can cause the metal plating to wear, which not only leads to unreality. The topographical image, and the rapid consumption of the probe also increases the cost of the study. The invention will greatly reduce the rapid wear of the needle tip and prolong the service life of the probe. (2) Currently, commercially available conductive AFM probes have diamond probes that use a stable diamond coating. Although the probe is low in wear, it increases the radius of the probe and reduces its lateral resolution. The present invention will maintain a smaller tip radius of curvature of the tip to maintain the probe with a high resolution. (3) Other solid metal or diamond coatings greatly increase the cost price of the probe. The present invention uses low-cost graphene as a cladding material, which greatly reduces the manufacturing cost. (4) Other conductive AFM probes may cause metal atoms of the plating layer to infiltrate the sample to introduce contamination of the sample. The present invention is incapable of imposing the impermeability of the graphene honeycomb structure and the strong atomic bond energy between the carbon atoms. Move to the sample to avoid contamination of the sample. (5) For chemical vapor deposition, the preparation of high quality graphene is very strong for its growth substrate. Selectivity, while the common AFM tip is not a benign substrate for graphene growth, so a new approach to preparing high quality graphene coated AFM tips is needed. The invention coats the high quality graphene on the AFM needle tip to avoid the adverse effects caused by the poor quality of the graphene.
本发明的目的可以通过以下技术方案实现：The object of the present invention can be achieved by the following technical solutions:
一种石墨烯包覆原子力显微镜探针，包括探针基底，悬臂，针尖，所述的悬臂和针尖上设有金属层，针尖上还设有石墨烯层。A graphene-coated atomic force microscope probe comprises a probe substrate, a cantilever, a needle tip, a metal layer on the cantilever and the needle tip, and a graphene layer on the needle tip.
优选的，所述的一种石墨烯包覆原子力显微镜探针，所述的金属层为双金属层，由内至外分别为钛和铂；或所述的金属层为单金属层，单金属为铂和铱的合金。Preferably, the graphene coated atomic force microscope probe, the metal layer is a bimetal layer, titanium and platinum respectively from the inside to the outside; or the metal layer is a single metal layer, a single metal It is an alloy of platinum and rhodium.
优选的，所述的一种石墨烯包覆原子力显微镜探针，所述的石墨烯层为1至3层，厚度为0.34-1nm。Preferably, the graphene coated atomic force microscope probe has a graphene layer of 1 to 3 layers and a thickness of 0.34-1 nm.
优选的，所述的一种石墨烯包覆原子力显微镜探针，所述的探针基底为硅或氮化硅。Preferably, the graphene is coated with an atomic force microscope probe, and the probe substrate is silicon or silicon nitride.
一种石墨烯包覆原子力显微镜探针的制备方法，所述的制备方法包括以下步骤：A method for preparing a graphene-coated atomic force microscope probe, the preparation method comprising the following steps:
(1)石墨烯溶液的制备：将5-10mg石墨烯加入1mL水中，在超声波清洗仪中超声分散10min，制备得到浓度为5-10mg/mL的石墨烯溶液；(1) Preparation of graphene solution: 5-10 mg of graphene is added to 1 mL of water, and ultrasonically dispersed in an ultrasonic cleaner for 10 min to prepare a graphene solution having a concentration of 5-10 mg/mL;
(2)制备石墨烯包覆原子力显微镜探针：将悬臂和针尖上设有金属层的原子力显微镜探针的针尖浸入步骤(1)的石墨烯溶液中，机械搅拌30-60s后取出自然晾干。(2) Preparation of graphene-coated atomic force microscope probe: The tip of the atomic force microscope probe provided with the metal layer on the cantilever and the needle tip is immersed in the graphene solution of the step (1), mechanically stirred for 30-60 seconds, and then taken out and naturally dried. .
所述的一种石墨烯包覆原子力显微镜探针的制备方法中步骤(1)制备的石墨烯溶液中石墨烯平均尺寸低于1微米，厚度为1-5层，每层厚度为0.334nm。The graphene prepared by the step (1) in the preparation method of the graphene-coated atomic force microscope probe has an average graphene size of less than 1 micrometer and a thickness of 1-5 layers, and each layer has a thickness of 0.334 nm.
所述的一种石墨烯包覆原子力显微镜探针的制备方法，制备方法中所述的金属层为双金属层，由内至外分别为钛和铂；或所述的金属层为单金属层，单金属为铂和铱的合金。The method for preparing a graphene-coated atomic force microscope probe, wherein the metal layer is a bimetal layer, and titanium and platinum are respectively from the inside to the outside; or the metal layer is a single metal layer. The single metal is an alloy of platinum and rhodium.
所述的一种石墨烯包覆原子力显微镜探针在制备原子力显微镜中的用途。The use of the graphene coated atomic force microscope probe for preparing an atomic force microscope.
石墨烯具有很大的比表面积和很好的柔韧性及延展性，使其可借助于范德华力的作用牢固地吸附在探针表面，从而可实现针尖被石墨烯层完全包覆的目的。Graphene has a large specific surface area and good flexibility and ductility, so that it can be firmly adsorbed on the surface of the probe by means of van der Waals force, so that the tip of the needle can be completely covered by the graphene layer.
后续处理的技术手段及其作用：观察石墨烯在AFM针尖上的附着状态及数量的多少，并用氮气对其探针针尖施加一定的作用力，这样一方面可以使石墨烯在针尖部位的吸附更加牢固，另一方面探针其他部位多余的石墨烯可以被除去。The technical means of subsequent processing and its role: observe the adhesion state and quantity of graphene on the tip of the AFM, and apply a certain force to the tip of the probe with nitrogen, so that the adsorption of graphene on the needle tip can be further improved. Firm, on the other hand, excess graphene in other parts of the probe can be removed.
本发明与现有技术相比，其有益效果为：Compared with the prior art, the invention has the following beneficial effects:
首先可以降低科研成本，延长探针的使用寿命，可进行多次实验，从而减少探针的损耗。其次增加了测试数据的可靠性，石墨烯AFM探针不会污染样品，能够提供真实的图像。First, the cost of research can be reduced, the life of the probe can be extended, and multiple experiments can be performed to reduce the loss of the probe. Secondly, the reliability of the test data is increased, and the graphene AFM probe does not contaminate the sample and can provide a real image.
社会经济效益：Social and economic benefits:
降低石墨烯探针的制造成本，制备方法简单，快捷，成本低，且原料能够多次利用。其次易产业化应用，制备过程不需人力，可全部实现自动化操作，并且产品能够满足供需。 The manufacturing cost of the graphene probe is reduced, the preparation method is simple, fast, and the cost is low, and the raw material can be utilized multiple times. Secondly, it is easy to industrialize and apply. The preparation process does not require manpower, and all of them can be automated, and the products can meet the supply and demand.
本发明石墨烯包覆AFM探针制备方法与现有技术制备方法(CVD法，刻蚀法，转移法)相比较有明显的优势：1.该技术不需要专业设备，如光刻机，CVD***等；2.不需要苛刻的条件，对制备条件无任何限制，如高温，惰性气氛环境；3.不涉及气体及有毒过程，如氮气，氩气，一氧化碳，光刻胶，丙酮等；4.不需要专业技术操作，如光刻及刻蚀，CVD气体控制等。总体来说，该制备技术方法简单，效果突出，且降低加工成本，易于产业化。The method for preparing the graphene-coated AFM probe of the invention has obvious advantages compared with the prior art preparation method (CVD method, etching method, transfer method): 1. The technology does not require professional equipment, such as a lithography machine, CVD System, etc.; 2. No harsh conditions, no restrictions on the preparation conditions, such as high temperature, inert atmosphere; 3. No gas and toxic processes, such as nitrogen, argon, carbon monoxide, photoresist, acetone, etc.; No professional technical operations such as photolithography and etching, CVD gas control, etc. are required. In general, the preparation technique is simple, the effect is outstanding, the processing cost is reduced, and the industrialization is easy.
附图说明DRAWINGS
图1为不含石墨烯层的镀铂-钛原子力显微镜探针的SEM图。Figure 1 is an SEM image of a platinum-titanium atomic force microscope probe without a graphene layer.
图2为石墨烯包覆的镀铂-钛原子力显微镜探针的SEM图。2 is an SEM image of a graphene coated platinum-titanium atomic force microscope probe.
图3为石墨烯包覆的镀铂-钛原子力显微镜探针针尖的局部TEM图像。Figure 3 is a partial TEM image of a graphene coated platinum-titanium atomic force microscope probe tip.
图4为不含石墨烯层的镀铂-钛原子力显微镜探针在扫描前后采集的电流-电压谱线。Figure 4 is a current-voltage line taken before and after scanning of a platinum-plated titanium atomic force microscope probe without a graphene layer.
图5为石墨烯包覆的镀铂-钛原子力显微镜探针在扫描前后采集的电流-电压谱线。Figure 5 is a current-voltage line taken before and after scanning of a graphene-coated platinum-titanium atomic force microscope probe.
图6为不含石墨烯层的导电原子力显微镜探针和不同方法制备的石墨烯包覆的原子力显微镜探针多次实验得出的总扫描面积统计图。Fig. 6 is a graph showing the total scan area obtained by a plurality of experiments conducted by a conductive atomic force microscope probe without a graphene layer and a graphene-coated atomic force microscope probe prepared by a different method.
图7为本发明的石墨烯包覆原子力显微镜探针的示意图。Figure 7 is a schematic illustration of a graphene coated atomic force microscope probe of the present invention.
附图说明中，所述的镀铂-钛原子力显微镜探针即为由内至外分别为钛和铂的双金属层的原子力显微镜探针。In the description of the drawings, the platinum-titanium atomic force microscope probe is an atomic force microscope probe of a bimetal layer of titanium and platinum, respectively, from the inside to the outside.
具体实施方式detailed description
实施例1Example 1
(1)石墨烯溶液的制备：将5mg石墨烯加入1mL水中，在超声波清洗仪中超声分散10min，制备得到浓度为5mg/mL的石墨烯溶液；(1) Preparation of graphene solution: 5 mg of graphene was added to 1 mL of water, and ultrasonically dispersed in an ultrasonic cleaner for 10 min to prepare a graphene solution having a concentration of 5 mg/mL;
(2)制备石墨烯包覆原子力显微镜探针：将基底为硅、悬臂和针尖上设有由内至外分别为钛和铂的双金属层的原子力显微镜探针的针尖浸入步骤(1)的石墨烯溶液中，机械搅拌60s后取出自然晾干。制备得的石墨烯包覆原子力显微镜探针中石墨烯层为1层，厚度为0.34nm。实施例2(2) Preparation of graphene-coated atomic force microscope probe: The tip of the atomic force microscope probe having the base of silicon, the cantilever and the tip of the needle provided with a bimetal layer of titanium and platinum respectively from the inside to the outside is immersed in the step (1) In the graphene solution, after mechanical stirring for 60 s, it was taken out and naturally dried. The prepared graphene-coated atomic force microscope probe has a graphene layer of 1 layer and a thickness of 0.34 nm. Example 2
(1)石墨烯溶液的制备：将10mg石墨烯加入1mL水中，在超声波清洗仪中超声分散10min，制备得到浓度为10mg/mL的石墨烯溶液；(1) Preparation of graphene solution: 10 mg of graphene was added to 1 mL of water, and ultrasonically dispersed in an ultrasonic cleaner for 10 min to prepare a graphene solution having a concentration of 10 mg/mL;
(2)制备石墨烯包覆原子力显微镜探针：将基底为氮化硅、悬臂和针尖上设有铂铱合金的单金属层的原子力显微镜探针的针尖浸入步骤(1)的石墨烯溶液中，机械搅拌30s后取出自然晾干。制备得到的石墨烯包覆原子力显微镜探针中石墨烯层为3层，厚度为1nm。(2) Preparation of graphene-coated atomic force microscope probe: The tip of the atomic force microscope probe having a single metal layer provided with silicon nitride, a cantilever and a needle tip on a platinum alloy is immersed in the graphene solution of the step (1). After mechanical stirring for 30 seconds, take it out and dry it naturally. The obtained graphene-coated atomic force microscope probe has a graphene layer of 3 layers and a thickness of 1 nm.
实施例3Example 3
(1)石墨烯溶液的制备：将7mg石墨烯加入1mL水中，在超声波清洗仪中超声分散10min， 制备得到浓度为7mg/mL的石墨烯溶液；(1) Preparation of graphene solution: 7 mg of graphene was added to 1 mL of water and ultrasonically dispersed for 10 min in an ultrasonic cleaner. Preparing a graphene solution having a concentration of 7 mg/mL;
(2)制备石墨烯包覆原子力显微镜探针：将基底为硅、悬臂和针尖上设有由内至外分别为钛和铂的双金属层的原子力显微镜探针的针尖浸入步骤(1)的石墨烯溶液中，机械搅拌45s后取出自然晾干。制备得到的石墨烯包覆原子力显微镜探针中石墨烯层为2层，厚度为0.68nm。(2) Preparation of graphene-coated atomic force microscope probe: The tip of the atomic force microscope probe having the base of silicon, the cantilever and the tip of the needle provided with a bimetal layer of titanium and platinum respectively from the inside to the outside is immersed in the step (1) In the graphene solution, after mechanical stirring for 45 s, it was taken out and naturally dried. The prepared graphene-coated atomic force microscope probe has two graphene layers and a thickness of 0.68 nm.
实施例4Example 4
(1)石墨烯溶液的制备：将7mg石墨烯加入1mL水中，在超声波清洗仪中超声分散10min，制备得到浓度为7mg/mL的石墨烯溶液；(1) Preparation of graphene solution: 7 mg of graphene was added to 1 mL of water, and ultrasonically dispersed in an ultrasonic cleaner for 10 min to prepare a graphene solution having a concentration of 7 mg/mL;
(2)制备石墨烯包覆原子力显微镜探针：将基底为硅、悬臂和针尖上设有铂铱单金属层的原子力显微镜探针的针尖浸入步骤(1)的石墨烯溶液中，机械搅拌45s后取出自然晾干。制备得到的石墨烯包覆原子力显微镜探针中石墨烯层为2层，厚度为0.68nm。(2) Preparation of graphene-coated atomic force microscope probe: The tip of the atomic force microscope probe with a platinum-ruthenium single metal layer on the substrate, silicon, cantilever and tip is immersed in the graphene solution of step (1), mechanically stirred for 45 s. Remove and let dry naturally. The prepared graphene-coated atomic force microscope probe has two graphene layers and a thickness of 0.68 nm.
实施例5Example 5
CVD法制备石墨烯AFM探针：乙醇作为碳源，金作为催化剂，氢气和氩气混合气作为载流气体。乙醇放置在低温区内，镀金AFM探针放置在高温区(750-850℃)，通入在标况下流速为100mL/min的混合气。5分钟后，在金表面形成石墨烯层。A graphene AFM probe was prepared by a CVD method: ethanol as a carbon source, gold as a catalyst, and a mixed gas of hydrogen and argon as a carrier gas. The ethanol was placed in a low temperature zone, and the gold-plated AFM probe was placed in a high temperature zone (750-850 ° C), and a mixture of a flow rate of 100 mL/min under standard conditions was introduced. After 5 minutes, a graphene layer was formed on the gold surface.
实施例6Example 6
刻蚀-CVD法制备石墨烯AFM探针：该方法第一步用氢氧化钠选择性刻蚀硅片，形成热的氧化层，再在其表面镀上铜作为石墨烯沉积的基底；第二步，通过化学气相沉积法在基底上得到连续的石墨烯层；第三步，使用SU-8光刻胶填充针尖模子，进行曝光显影操作；第四步，通入干燥的氩气除去表面没有光刻胶的石墨烯区域，同时，旋涂第二层SU-8光刻胶以形成探针的悬臂。最后，除去针尖背面多余的氧化硅等，清洗剩余部分，从而得到整个AFM探针。Etching-CVD method for preparing graphene AFM probe: the first step of the method is to selectively etch silicon wafer with sodium hydroxide to form a hot oxide layer, and then plate copper on the surface as a substrate for graphene deposition; Step, obtaining a continuous graphene layer on the substrate by chemical vapor deposition; in the third step, filling the needle tip mold with SU-8 photoresist, performing exposure development operation; and fourth step, removing dry argon gas to remove the surface The graphene region of the photoresist is simultaneously spin coated with a second layer of SU-8 photoresist to form the cantilever of the probe. Finally, excess silicon oxide or the like on the back surface of the needle tip is removed, and the remaining portion is washed to obtain the entire AFM probe.
实施例7Example 7
转移法制备石墨烯AFM探针：首先在铜基石墨烯上旋涂一层PMMA，后用三氯化铁溶液刻蚀铜基底，分别用盐酸和水溶液清洗后得到PMMA/石墨烯层；导电AFM探针作为接收石墨烯的基底，转移后晾一段时间至干燥(石墨烯附着在探针表面)后用丙酮除去PMMA，最后用水清洗即可得到石墨烯覆盖的AFM探针。Preparation of graphene AFM probe by transfer method: firstly, a layer of PMMA is spin-coated on copper-based graphene, and then the copper substrate is etched with ferric chloride solution, and then washed with hydrochloric acid and aqueous solution to obtain PMMA/graphene layer; conductive AFM The probe serves as a substrate for receiving graphene. After transfer, it is left to dry for a period of time until the graphene is attached to the surface of the probe. The PMMA is removed by acetone, and finally washed with water to obtain a graphene-covered AFM probe.
表征工具：扫描电子显微镜(SEM)，透射电子显微镜(TEM)，导电原子力显微镜(CAFM)表征方法：Characterization tools: scanning electron microscopy (SEM), transmission electron microscopy (TEM), conductive atomic force microscopy (CAFM) characterization methods:
1)将制备的不含石墨烯层的由内至外分别为钛和铂的双金属层的原子力显微镜探针和石墨烯包覆原子力显微镜探针进行SEM和TEM形貌表征，得到相应的图像，从中可清晰地观察到 探针针尖被石墨烯包覆前后的对比效果。图1和图2直观地看出不含石墨烯层的由内至外分别为钛和铂的双金属层的原子力显微镜探针针尖磨损程度很大，石墨烯包覆AFM探针针尖磨损程度小。图3中石墨烯片层覆盖在针尖上。1) Atomic force microscopy probes and graphene coated atomic force microscopy probes of a bimetallic layer containing titanium and platinum, respectively, which are free of graphene layers, are characterized by SEM and TEM, and corresponding images are obtained. From which it can be clearly observed The contrast effect of the probe tip before and after being coated with graphene. Figure 1 and Figure 2 visually show that the atomic force microscopy probe tip of the bimetal layer containing titanium and platinum, which does not contain a graphene layer, is highly worn, and the tip of the graphene-coated AFM probe has a small degree of wear. . The graphene sheet in Figure 3 covers the tip of the needle.
2)CAFM表征：铜基单层石墨烯作为扫描样品，分别用不含石墨烯层的由内至外分别为钛和铂的双金属层的原子力显微镜探针和利用本发明技术手段制备的石墨烯包覆原子力显微镜探针进行不间断扫描测试，在相同的测试条件下，进行多次扫描直至探针失去导电性。2) CAFM characterization: copper-based single-layer graphene as a scanning sample, using atomic force microscope probes containing a graphene layer and a bimetal layer of titanium and platinum, respectively, from the inside to the outside, and graphite prepared by the technical means of the present invention The ene coated AFM probe was subjected to an uninterrupted scanning test, and under the same test conditions, multiple scans were performed until the probe lost conductivity.
从图4和图5中可看出在扫描样品之前探针与样品之间均为欧姆接触，在扫描结束之后，不含石墨烯层的由内至外分别为钛和铂的双金属层的原子力显微镜探针与样品之间形成较高的肖特基势垒(针尖磨损程度高)，而石墨烯包覆探针有较低的肖特基势垒(针尖磨损程度低)，因此，石墨烯大大降低了探针的磨损程度，从SEM图中也可直观得到此结果。It can be seen from Fig. 4 and Fig. 5 that the probe is in ohmic contact with the sample before scanning the sample, and after the end of the scanning, the bimetal layer of titanium and platinum is not contained in the graphene layer from the inside to the outside. A high-order Schottky barrier is formed between the AFM probe and the sample (high degree of tip wear), while the graphene-coated probe has a lower Schottky barrier (lower tip wear), therefore, graphite The olefin greatly reduces the degree of wear of the probe, and this result can also be visually obtained from the SEM image.
实验结果显示：石墨烯包覆AFM探针可测得的总扫描面积是不含石墨烯层的由内至外分别为钛和铂的双金属层的原子力显微镜探针能够测得的总扫描面积6-10倍。图6比较了不含石墨烯层的由内至外分别为钛和铂的双金属层的原子力显微镜探针和由不同方法制得的石墨烯AFM探针多次实验得出的总扫描面积统计图，结果显示，本发明技术制备的石墨烯AFM探针的导电性能整体高于其他方法制得的石墨烯AFM探针和不含石墨烯层的镀铂-钛原子力显微镜探针和其他方法制备的石墨烯探针，具有最长的使用寿命。 The experimental results show that the total scan area measured by the graphene-coated AFM probe is the total scan area that can be measured by an atomic force microscope probe with a graphene layer and a bimetal layer of titanium and platinum, respectively. 6-10 times. Figure 6 compares the total scan area statistics obtained by atomic force microscopy probes of graphene-free bimetal layers with titanium and platinum, respectively, and graphene AFM probes prepared by different methods. The results show that the graphene AFM probe prepared by the technique of the present invention has higher electrical conductivity than the graphene AFM probe prepared by other methods and the platinum-titanium atomic force microscope probe without graphene layer and other methods. Graphene probes have the longest lifespan.

Claims (8)

  1. 一种石墨烯包覆原子力显微镜探针，包括探针基底，悬臂，针尖，其特征在于，所述的悬臂和针尖上设有金属层，针尖上还设有石墨烯层。A graphene-coated atomic force microscope probe comprising a probe substrate, a cantilever, and a needle tip, wherein the cantilever and the needle tip are provided with a metal layer, and the tip of the needle is further provided with a graphene layer.
  2. 根据权利要求1所述的一种石墨烯包覆原子力显微镜探针，其特征在于：所述的金属层为双金属层，由内至外分别为钛和铂；或所述的金属层为单金属层，单金属为铂和铱的合金。The graphene-coated atomic force microscope probe according to claim 1, wherein the metal layer is a bimetal layer, and titanium and platinum are respectively from the inside to the outside; or the metal layer is a single The metal layer, the single metal is an alloy of platinum and rhodium.
  3. 根据权利要求1所述的一种石墨烯包覆原子力显微镜探针，其特征在于，所述的石墨烯层为1至3层，厚度为0.34-1nm。The graphene-coated atomic force microscope probe according to claim 1, wherein the graphene layer is 1 to 3 layers and has a thickness of 0.34-1 nm.
  4. 根据权利要求1所述的一种石墨烯包覆原子力显微镜探针，其特征在于，所述的探针基底为硅或氮化硅。A graphene-coated atomic force microscope probe according to claim 1, wherein said probe substrate is silicon or silicon nitride.
  5. 一种石墨烯包覆原子力显微镜探针的制备方法，其特征在于所述的制备方法包括以下步骤：A method for preparing a graphene-coated atomic force microscope probe, characterized in that the preparation method comprises the following steps:
    (1)石墨烯溶液的制备：将5-10mg石墨烯加入1mL水中，在超声波清洗仪中超声分散10min，制备得到浓度为5-10mg/mL的石墨烯溶液；(1) Preparation of graphene solution: 5-10 mg of graphene is added to 1 mL of water, and ultrasonically dispersed in an ultrasonic cleaner for 10 min to prepare a graphene solution having a concentration of 5-10 mg/mL;
    (2)制备石墨烯包覆原子力显微镜探针：将悬臂和针尖上设有金属层的原子力显微镜探针的针尖浸入步骤(1)的石墨烯溶液中，机械搅拌30-60s后取出自然晾干。(2) Preparation of graphene-coated atomic force microscope probe: The tip of the atomic force microscope probe provided with the metal layer on the cantilever and the needle tip is immersed in the graphene solution of the step (1), mechanically stirred for 30-60 seconds, and then taken out and naturally dried. .
  6. 根据权利要求5所述的一种石墨烯包覆原子力显微镜探针的制备方法，其特征在于步骤(1)制备的石墨烯溶液中石墨烯平均尺寸低于1微米，厚度为1-5层，每层厚度为0.334纳米。The method for preparing a graphene-coated atomic force microscope probe according to claim 5, wherein the graphene solution prepared in the step (1) has an average graphene size of less than 1 micrometer and a thickness of 1-5 layers. Each layer has a thickness of 0.334 nm.
  7. 根据权利要求5所述的一种石墨烯包覆原子力显微镜探针的制备方法，其特征在于所述的金属层为双金属层，由内至外分别为钛和铂；或所述的金属层为单金属层，单金属为铂和铱的合金。The method for preparing a graphene-coated atomic force microscope probe according to claim 5, wherein the metal layer is a bimetal layer, and titanium and platinum are respectively from the inside to the outside; or the metal layer As a single metal layer, the single metal is an alloy of platinum and rhodium.
  8. 根据权利要求1至4任一所述的一种石墨烯包覆原子力显微镜探针在制备原子力显微镜中的用途。 Use of a graphene-coated atomic force microscope probe according to any one of claims 1 to 4 for the preparation of an atomic force microscope.
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