WO2014090938A1 - Pointes de microscope à force atomique conducteur (cafm) revêtues de graphène - Google Patents

Pointes de microscope à force atomique conducteur (cafm) revêtues de graphène Download PDF

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Publication number
WO2014090938A1
WO2014090938A1 PCT/EP2013/076362 EP2013076362W WO2014090938A1 WO 2014090938 A1 WO2014090938 A1 WO 2014090938A1 EP 2013076362 W EP2013076362 W EP 2013076362W WO 2014090938 A1 WO2014090938 A1 WO 2014090938A1
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WO
WIPO (PCT)
Prior art keywords
graphene
probe
force microscope
atomic force
layer
Prior art date
Application number
PCT/EP2013/076362
Other languages
English (en)
Inventor
Huiling DUAN
Marc PORTI PUJAL
Mario LANZA MARTINEZ
Albin BAYERL
Montserrat NAFRÍA MAQUEDA
Original Assignee
Universitat Autonoma De Barcelona
Peking University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universitat Autonoma De Barcelona, Peking University filed Critical Universitat Autonoma De Barcelona
Publication of WO2014090938A1 publication Critical patent/WO2014090938A1/fr

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Classifications

    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q70/00—General aspects of SPM probes, their manufacture or their related instrumentation, insofar as they are not specially adapted to a single SPM technique covered by group G01Q60/00
    • G01Q70/08—Probe characteristics
    • G01Q70/14—Particular materials

Definitions

  • the present patent application is related to conductive atomic force microscope tips, and has remarkable advantages. More specifically, the present invention relates to coating with a graphene single layer film the conductive surface of an atomic force microscope tip, leading to a much more resistant to both high currents and frictions than commercially available metal-varnished CAFM tips, and also to much larger lifetimes and more reliable imaging due to a lower tip-sample interaction.
  • a good approach to preserve CAFM tip properties is to varnish them with a very stable material, such as doped diamond.
  • a very stable material such as doped diamond.
  • this approach not only reduces the lateral resolution of measurement (due to a larger tip radius), but also increases the price of the tips.
  • solid metallic AFM tips Therefore, finding a new method to avoid fast tip wearing is essential for cheap and reliable nanoscale electrical characterization.
  • graphene (a two-dimensional sheet of carbon atoms arranged in a dense honeycomb lattice) is a material that has excellent mechanical, physical and electronic properties.
  • the only known method to obtain graphene was from mechanical exfoliation (repeated peeling) of small mesas of highly oriented pyrolytic graphite, and it was mainly used as a conductive channel in Field Effect Transistors.
  • the new method to produce graphene by Chemical Vapor Deposition (CVD) is a revolutionary approach for graphene growth and manipulation, since, by CVD, graphene can not only be grown on different substrates but is also transferrable to arbitrary substrates. This method extends the use of graphene to other applications, for example commercially available CAFM tip being coated with a sheet of CVD-grown graphene.
  • the nickel layer can be made by thermal evaporation or sputtering and the graphene layer is made by Chemical Vapor Deposition (CVD).
  • the graphene layer can be a multi or single layer. There is no disclosure about a particular process involving polymeric intermediate layers dissolved or etched by acetone, in liquid or in vapor state.
  • This conductive Pt-lr alloy external layer would offer better properties versus the state of the art (gold-coated silicon AFM-tip coated with a graphene multilayer by CVD, or totally metallic tip) in terms of economic cost, and in terms of dimensions variation respect the original shape of the commercial tip. DESCRIPTION OF THE INVENTION
  • the present invention has been developed with the aim of improving the performance of the conductive atomic force microscope tips, expecting that such invention will be a novelty in the field of the application of such technology, resolving the current disadvantages mentioned above, and presenting further additional advantages that will be evident from the following description.
  • the resulting tip will be totally coated with graphene, and therefore much more resistant to both high currents and frictions than commercially available metal-varnished CAFM tips, and also to much larger lifetimes and more reliable imaging due to a lower tip-sample interaction.
  • the invention is related to a graphene coating process of a probe for an atomic force microscope comprising a step of transference of a graphene layer from a metal substrate to a polymeric substrate, further comprising the steps of:
  • the polymeric layers work as holding means during the process, immobilizing the probe for the purpose of a proper deposition of the graphene layer on the probe's external surface.
  • the graphene layer is a single atomic sheet. In this way the additional layer minimizes the dimensional variation of the probe tip.
  • the coating of the base by a first polymeric layer is carried out by a spin coating technique, which has the advantage of producing a uniform thin film (thicknesses -200 nm) in flat substrates. This is achieved rotating at high speed the substrate in order to spread the fluid place on it by centrifugal force. With this technique it is possible to dimension very precisely the thicknesses of this first polymeric layer, which is useful in terms to define the time necessary to be solved, in relation to what it is needed with the other polymeric layers of the sample structure.
  • the probe comprises a support, a cantilever, and a tip, and it is the bottom surface of said support the part attached to the first polymeric layer.
  • the coating of the probe by a second polymeric layer may be carried out specifically by a drop casting technique, which has the advantage the polymer fills the gap under the cantilever and the tip.
  • the deposition of said polymeric substrate with a graphene layer over said second polymeric layer is carried out typically inside water, or another similar inert liquid. More specifically the graphene layer (still attached its substrate polymeric layer) rests over the water surface in a recipient. The probe, already covered with the intermediate polymeric layer, will be manipulated to come up from inside of the liquid and to pick up the graphene layer with its substrate polymeric layer attached.
  • the polymer of the polymeric layers is Poly-methyl methacrylate (PMMA) due to its suitable properties for this process.
  • the solvent agent is acetone also due to its suitable properties for this process.
  • the dissolving step is carried out inside a camera with acetone steam, and more particularly over a boiling acetone container. Being exposed the structure Graphene/PMMA/AFM tip/PMMA/Base just to vaporized acetone, all the PMMA layers will be dissolved gradually and simultaneously without losing a substantive horizontal position, and therefore avoiding its slippage into the boiling acetone.
  • the graphene coated probe will rest on the base being ready to be easily picked up.
  • the camera serves as vapor enclosure to increase etching yield and constant etching on the entire sample.
  • the camera remains open on the top to avoid that drops of condensed acetone precipitate on the sample.
  • the dissolving step is carried out over a period of approximately 30 minutes to assure the smoothness of the etching process, and to avoid falls and breakages of the probe.
  • the graphene coated probe itself comprises a support, a cantilever, and a tip, including, at least the tip, a silicon substrate varnished with a conductive layer of a Pt-lr alloy.
  • Said probe, Pt-lr alloy further coated with a graphene layer is cheaper than probes with other materials (as, for example, doped diamond) as conductive layer, and also cheaper than fully metallic AFM tips.
  • the graphene layer is a single atomic sheet, not having the probe tip any dimensional variation after being graphene coated.
  • FIG. 1 is a schematic view for illustrating an as-received commercial Pt-lr varnished probe
  • FIG. 2 is a schematic view for illustrating an as-grown GSL on both sides of a Cu foil
  • FIG. 3 is a schematic view for illustrating a sample of FIG. 2 covered on one side with spin coated PMMA;
  • FIG. 4 is a schematic view for illustrating a sample of FIG. 3 wherein the bottom GSL and the Cu foil are etched;
  • FIG. 5 is a schematic view for illustrating a base, typically a piece of Silicon, covered with spin coated PMMA;
  • FIG. 6 is a schematic view for illustrating a sample of FIG. 5 wherein the tip is attached on a heated first layer of PMMA in order to fix the structure;
  • FIG. 7 is a schematic view for illustrating a sample of FIG. 6 wherein the AFM tip / PMMA / Si structure is again coated with PMMA;
  • FIG. 8 is a schematic view for illustrating the Graphene/PMMA stack of FIG. 4 being transferred onto the sample of FIG. 7;
  • FIG. 9 is a schematic view for illustrating a sample of FIG. 8 with the PMMA removed using Acetone and maintaining the tip completely horizontal.
  • FIG. 10 is a schematic view for illustrating a home-made engine to remove all the PMMA layers while maintaining the sample completely horizontal.
  • One preferred implementation of the graphene coating process of a probe (1 ) for an atomic force microscope comprises a step of transference of a graphene layer (4) from a metal substrate (9) to a polymeric substrate (33), further comprising the steps of:
  • the coating of the base (2) by a first polymeric layer (31 ) is carried out by a spin coating technique.
  • the probe (1 ) comprises a support (13), a cantilever (12), and a tip (1 1 ), and in that the bottom surface of said support (13) is attached to the first polymeric layer (31 ) before it completely dries, such that the probe (1 ) stays in a substantially horizontal position. More specifically, the conditions of this part of the process are:
  • the solid PMMA/AFM tip/PMMA/Silicon block was created by:
  • the Silicon substrate was spin-covered with 200 nm of PMMA, (spinner working at 1000 rpm during 1 minute);
  • the AFM tip is attached and cured the whole structure for 10 minutes at 130 °C on a hot plate to immobilize it.
  • the AFM tip/PMMA/Silicon is again spin coated with 200 nm PMMA using the spinner and a hot plate.
  • Graphene over Cu is commercially available, but one possible growth process consists of: i) Load the cut Cu foil (25 ⁇ , Alfa Aesar) into the 25 mm inner tube, flush the chamber with 400 seem Ar and 50 seem H2 for 5min, close the gas flows and then pump the chamber down to 1 mTorr;
  • the coating of the probe (1 ) by a second polymeric layer (32) is carried out by a drop casting technique.
  • the deposition of said polymeric substrate (33) with a graphene layer (4) over said second polymeric layer (32) is carried out inside water.
  • the polymer of the polymeric layers (31 , 32, 33) is PMMA
  • the solvent agent (5) is acetone, being the dissolving step carried out inside a camera (6) with acetone steam (52), and more specifically over a boiling acetone container (7), lasting this dissolving step over a period of 30 minutes.
  • a probe (1 ) for an atomic force microscope comprising a support (13), a cantilever (12), and a tip (1 1 ), characterized in that at least the tip (1 1 ) includes a silicon substrate (81 ) varnished with a conductive layer (82) of a Pt-lr alloy, and further coated with a graphene layer (4), being preferably said graphene layer (4) a single atomic sheet.
  • the commercial tips are made by silicon micromachining and are coated first with a 20 nm thick layer of Pt-lr, which is a 95% Platinum and 5% Iridium alloy (the Iridium is used to enhance the stability of the Platinum layer).

Abstract

La présente invention concerne l'application en revêtement d'un film de monocouche de graphène à la surface conductrice d'une pointe de microscope à force atomique (AFM). Le processus de revêtement de la surface conductrice avec du graphène consiste en trois étapes : d'abord, immobilisation de la pointe sur un bloc de silicium en tant que base à l'aide d'un film mince de méthacrylate de polyméthyle (PMMA) entre ceux-ci. Ensuite, le PMMA/pointe AFM/PMMA/bloc de silicium a été utilisé en tant que substrat de cible sur lequel est transférée la feuille de graphène. Finalement, les différentes couches de PMMA sont retirées à l'aide d'acétone. Une fois que le PMMA est retiré, le graphène est complètement fixé. La pointe résultante est parfaitement revêtue de graphène et ainsi beaucoup plus résistante à la fois à des courants et des frottements élevés que des pointes AFM conducteur (CAFM) vernies de métal disponibles commercialement, et également des durées de vie beaucoup plus grandes et une imagerie plus fiable en raison d'une interaction pointe-échantillon plus faible.
PCT/EP2013/076362 2012-12-14 2013-12-12 Pointes de microscope à force atomique conducteur (cafm) revêtues de graphène WO2014090938A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12382504.4 2012-12-14
EP12382504 2012-12-14

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WO2014090938A1 true WO2014090938A1 (fr) 2014-06-19

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104360107A (zh) * 2014-11-12 2015-02-18 苏州大学 一种石墨烯包覆原子力显微镜探针及其制备方法、用途
CN108658037A (zh) * 2018-04-27 2018-10-16 国家纳米科学中心 一种石墨烯功能化纳米针尖及其制备方法
CN109030870A (zh) * 2018-07-19 2018-12-18 清华大学 二维层状材料包裹原子力显微镜探针及其制备方法以及应用
CN110488044A (zh) * 2019-07-29 2019-11-22 清华大学 一种实现锥形针尖的afm探针与石墨表面之间超滑的方法
US10545172B2 (en) 2016-03-17 2020-01-28 National University Corporation Nagoya Institute Of Technology Cantilever and manufacturing method for cantilever

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104360107A (zh) * 2014-11-12 2015-02-18 苏州大学 一种石墨烯包覆原子力显微镜探针及其制备方法、用途
WO2016074305A1 (fr) * 2014-11-12 2016-05-19 苏州大学张家港工业技术研究院 Sonde de microscope à force atomique revêtue de graphène, procédé de fabrication et application correspondants
US10545172B2 (en) 2016-03-17 2020-01-28 National University Corporation Nagoya Institute Of Technology Cantilever and manufacturing method for cantilever
CN108658037A (zh) * 2018-04-27 2018-10-16 国家纳米科学中心 一种石墨烯功能化纳米针尖及其制备方法
CN109030870A (zh) * 2018-07-19 2018-12-18 清华大学 二维层状材料包裹原子力显微镜探针及其制备方法以及应用
CN110488044A (zh) * 2019-07-29 2019-11-22 清华大学 一种实现锥形针尖的afm探针与石墨表面之间超滑的方法

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