Friction-induced nanofabrication method to produce protrusive nanostructures on quartz
© Song et al; licensee Springer. 2011
Received: 27 October 2010
Accepted: 7 April 2011
Published: 7 April 2011
In this paper, a new friction-induced nanofabrication method is presented to fabricate protrusive nanostructures on quartz surfaces through scratching a diamond tip under given normal loads. The nanostructures, such as nanodots, nanolines, surface mesas and nanowords, can be produced on the target surface by programming the tip traces according to the demanded patterns. The height of these nanostructures increases with the increase of the number of scratching cycles or the normal load. Transmission electron microscope observations indicated that the lattice distortion and dislocations induced by the mechanical interaction may have played a dominating role in the formation of the protrusive nanostructures on quartz surfaces. Further analysis reveals that during scratching, a contact pressure ranged from 0.4P y to P y (P y is the critical yield pressure of quartz) is apt to produce protuberant nanostructures on quartz under the given experimental conditions. Finally, it is of great interest to find that the protrusive nanostructures can be selectively dissolved in 20% KOH solution. Since the nanowords can be easily 'written' by friction-induced fabrication and 'erased' through selective etching on a quartz surface, this friction-induced method opens up new opportunities for future nanofabrication.
Due to its high fundamental frequencies, high Q property and excellent piezoelectric behaviour, quartz has been widely used to produce sensors in micro/nano electromechanical systems (MEMS/NEMS), such as accelerometer, pressure sensor, gyro sensor, crystal oscillator and tuning fork biosensor, etc. [1–5]. Moreover, quartz is also an ideal substrate material for MEMS/NEMS because of its well-known electrical insulation and chemical stability . As the scale-down of device dimensions continues, it is essential to explore new nanofabrication methods, especially for nanoscale quartz devices.
General methods for the nanofabrication of quartz include chemical etching, plasma etching and reactive ion etching [7–9]. However, the use of these techniques tends to be limited by such disadvantages as environmental pollution, poor resolution and low efficiency . Focused ion beam (FIB) technology is advantageous for material processing at nanoscale because of its high machining precision , but the ion beam may cause undesirable materials degradation and the equipment is costly [12, 13]. In recent years, atomic force microscope (AFM) and scanning tunnelling microscope (STM) have been utilized for nanofabrication . The AFM tips are used as sharp tools to cut and remove materials, thus forming nano-grooves on the target surface . However, it is difficult, if not impossible, to fabricate protrusive nanostructures using AFM. Combining anodic oxidation with STM can be used to process protuberant structures on the surfaces of conductors and semiconductors under a given voltage [16, 17]. Nevertheless, the anodic oxidation process is invalid for nonconductive STM tips or for insulator surfaces. Therefore, by virtue of the high precision and multifunction of AFM, it is of great importance to develop an accurate and straightforward method for fabricating protuberant nanostructures on insulator surfaces based on the proximal probe method.
In the present study, a new friction-induced nanofabrication method to produce protrusive nanostructures on a quartz surface has been developed by directly scratching a diamond tip on the quartz surface under a given normal load. The capability of this nanofabrication method has been demonstrated by various nanostructures including nanodots, nanolines, isolated mesas, nanowords and so on. The effect of the applied normal load and the number of scratching cycles on the height of nanolines was studied. The generation mechanism of the protuberant nanostructures was discussed and the chemical activity of nanolines on quartz was investigated. Clearly, the friction-induced nanofabrication method may shed new light on nanotechnology.
Material and experimental details
The monocrystalline quartz wafers (AT-cut) with a thickness of 0.5 mm were purchased from Semiconductor Wafer, Inc. (Hsinchu, Taiwan). By using an atomic force microscope (AFM, SPI3800N, Seiko, Tokyo, Japan), the root-mean-square (RMS) roughness of the quartz wafers was measured to be 0.25 nm over a 2 μm × 2 μm area. The chemical binding and crystal state of the quartz material were detected by an X-ray photoelectron spectroscope (XPS, XSAM 800, CRATOS CO., Manchester, UK) and an X-ray diffraction machine (XRD, Philips X'Pert PRO, PANalytical, Almelo, Netherlands), respectively. The results indicate that the monocrystalline quartz consists of pure SiO2 and its crystal plane is Before the fabrication, the quartz samples were ultrasonically cleaned in methanol, ethanol and deionized water for 10 min. To etch the quartz sample, a KOH solution (20% in weight) was prepared using solid KOH (analytical purity) and deionized water.
All the fabrications were performed by an AFM equipped with a vacuum chamber. If not specially mentioned, a pyramidal diamond tip (Micro Star Technologies, Huntsville, USA) with curvature radius R of 300 nm was used for fabrication. The spring constant of the cantilever was calibrated as 203 N/m . After the fabrication, the topography of protrusive nanostructures was scanned in situ by a Si3N4 tip with a spring constant of 0.1 N/m (MLCT, Veeco, Plainview, USA). Two scratching modes were adopted in this study: bidirectional line-scratch for producing linear protrusive nanostructures and scanning-scratch for area protrusive nanostructures (surface mesas) [19–21]. The length of nanolines was controlled by the displacement amplitude D of the diamond tip on samples. If D shortens to several tens of nanometers under line-scratch, a nanodot would be made. In both modes, the scratching frequency was set at 2 Hz, the temperature was controlled at 20 ± 3°C and the relative humidity was ranged between 50 ± 5%.
To investigate the effect of the number of line-scratch cycles N on the generation of protrusive nanostructures, the scratching tests were performed on quartz surface under an applied normal load F n = 5 μN and various N between 10 and 150. Moreover, the effect of F n on the generation of protrusive nanostructures was studied by 100 line-scratch cycles on quartz surface under various F n of 3 to 26 μN. During the tests, the displacement amplitude of the line-scratch was 4 μm and the sliding speed was 32 μm/s if not specifically mentioned. Nanodots were produced by line-scratching with F n = 6 μN, N = 100 and D = 80 nm. The surface mesa with size of 3 μm × 3 μm was fabricated under F n = 6 μN and N = 4. By using a dull diamond tip with curvature radius of 500 nm, the letters 'NANO' were written at F n = 30 μN, N = 100. To understand the generation mechanism of the protrusive nanostructures, some nanolines were created on quartz surface in vacuum with a pressure better than 2.7 × 10-4 Pa.
Cross-sectional transmission electron microscope (XTEM) sample was prepared by Quanta 3D FEG FIB miller (FEI Company, Hillsboro, USA). Prior to milling, a protective platinum coating was deposited by 5 kV electron-beam firstly and then 30 kV at 0.5 nA ion-beam on the top of nanolines. Milling was performed with low beam currents from 15 to 5 nA at 30 kV and final thinning at 1 to 0.1 nA, 30 kV, finished with a final polish mills at 5 kV 48 pA. A JEOL JEM-2100 LaB6 TEM (JEOL Ltd., Tokyo, Japan) with the operating voltage of 80 kV was used to characterise the cross-sectional protrusive nanostructures.
Fabrication of nanolines on quartz surface
When scratching a surface using a sharp diamond tip, the generation of grooves was usually observed in the scratched area . However, protrusive nanostructures have been generated in the present study under the given conditions. Since the formation of the protrusive nanostructures on quartz surface has not been observed during indentation tests, the sliding and friction seem to be the necessary conditions for the generation of protrusive nanostructures. Therefore, the process can be viewed as friction-induced nanofabrication.
Fabrication of various nanostructures on quartz surface
Generation mechanism of the friction-induced nanostructures on quartz
It was reported that the protrusive nanostructures could also be produced by scratching on silicon surface [19, 20, 22]. Andoh and coworkers  suggested that the formation of silicon hillocks was mainly attributed to the chemical reactions in the atmosphere. However, our recent research indicated that the friction-induced silicon hillock can be fabricated in vacuum with a pressure better than 2.7 × 10-4 Pa . Based on the TEM observation on the cross-sectional microstructure of the silicon nanolines, mechanical interaction between the tip and the materials surfaces has been proved to play a dominant role in the generation of silicon hillocks [19, 20].
Critical contact stress for the fabrication of friction-induced hillock
With the equivalent elastic module E = 110.3 GPa [24, 26–28], the tip radius R = 300 nm and normal load F n = 3 to 67 μN, the contact pressure P c for the fabrication of protrusive nanostructures on quartz is calculated to be 4.3 to 12.1 GPa.
Therefore, it can be concluded that the contact pressure P c ranged from 0.4P y to P y is a feasible standard for friction-induced fabrication on a quartz surface under the given conditions. It reveals that the protrusive deformation is the initial surface damage during the nanowear on quartz. However, the surface damage of materials during nanowear process was not only depended on contact pressure P c, but also on the number of nanowear cycles N, displacement amplitude D, tribochemistry and other frictional factors [19, 20, 23, 30]. When the experimental conditions change, the critical P c of the formation of hillocks may vary. For example, because of the serious tribochemical reaction during the nanowear of Si/SiO2 pairs in air, the scratches appeared on the silicon surface while the contact pressure was only 0.13P y under the experimental conditions of N = 200 and D = 12.5 nm .
Selective etching of nanolines on quartz
In summary, the friction-induced method provides a manoeuvrable and direct way for fabricating protuberant nanostructures on quartz with high precision. Combining with the selective etching behaviour of the nanostructures, it is possible to develop a new nanofabrication technique on quartz.
A novel friction-induced nanofabrication method has been developed to produce protrusive nanostructures on nonconductive quartz material. Under the given conditions, the height of the nanolines on quartz surface increases sharply and then tends to stabilize with the increase of the normal load or the number of scratching cycles. Since the nanolines generated in atmosphere and vacuum were almost same under the same loading conditions, the creation of friction-induced nanostructures on quartz may be mainly attributed to the mechanical interaction. Based on the TEM observation, the lattice distortion and formation of dislocations induced by the mechanical interaction was suggested to be the main generation mechanism of the protrusive nanostructures on quartz surfaces. The detailed analysis based on the experimental results and stress calculation reveals that, during scratching, a contact pressure ranged from 0.4P y to P y (P y is the critical yield pressure of quartz) is apt to produce protuberant nanostructures under the given experimental conditions. Finally, the protrusive nanostructures can be selectively dissolved in 20 wt% KOH solution. Since the nanowords can be easily 'written' by friction-induced fabrication and 'erased' through selective etching, it may open up new opportunities for future nanofabrication on quartz.
atomic force microscope
focused ion beam
micro/nano electromechanical systems
selected-area electron diffraction
scanning tunnelling microscope
transmission electron microscope
X-ray photoelectron spectroscope
X-ray diffraction machine
cross-sectional transmission electron microscope.
The authors are grateful for the financial support from the National Basic Research Program (2011CB707604), Natural Science Foundation of China (90923017, 50625515, 50821063) and the Royal Society (UK) under China-UK Science Networks Scheme and the Royal Academy of Engineering (UK) under Research Exchanges with China Short Award.
- Lam CS: A Review of the recent development of MEMS and crystal oscillators and their impacts on the frequency control products industry. IEEE International Ultrasonics Symposium, Beijing, China 2008, 694–704.
- Santiram K, Soumen D: Development of silicon and quartz based MEMS high precision accelerometers. Indian J Pure Appl Phys 2007, 45: 299–303.
- Su XD, Dai CC, Zhang J, O'Shea SJ: Quartz tuning fork biosensor. Biosens Bioelectron 2002, 17: 111–117. 10.1016/S0956-5663(01)00249-4View Article
- Sagmeister BP, Graza IM, Schwödiauera R, Gruberb H, Bauera S: User-friendly, miniature biosensor flow cell for fragile high fundamental frequency quartz crystal resonators. Biosens Bioelectron 2009, 24: 2643–2648. 10.1016/j.bios.2009.01.023View Article
- Tanaka M: An industrial and applied review of new MEMS devices features. Microelectron Eng 2007, 84: 1341–1344. 10.1016/j.mee.2007.01.232View Article
- Cai HG, Yang ZQ, Ding GF, Zhao XL: Fabrication of a MEMS inertia switch on quartz substrate and evaluation of its threshold acceleration. Microelectron J 2008, 39: 1112–1119. 10.1016/j.mejo.2008.01.068View Article
- Iwata H: Multistage chemical etching for high-precision adjustment of resonance frequency in ultrahigh-frequency-fundamental quartz resonators. IEEE Trans Ultrason Ferroelectr Freq Control 2005, 52: 1435–1442. 10.1109/TUFFC.2005.1516014View Article
- Karre PSK, Cheam DD, Bergstrom PL: Realization of nano-wires in quartz using focused ion beam and ICP/RIE etching process for single electron transistor fabrication. 8th IEEE Conference on Nanotechnology, Arlington, USA 2008, 171–174.
- Yamada H, Kuwahara K, Fujiyama H: SiO 2 etching characteristics in DC magnetron plasmas by using an external magnetic field. Thin Solid Films 1998, 316: 6–12. 10.1016/S0040-6090(98)00379-4View Article
- Kim HS, Yoon JK, Lee YH, Ko YW, Park JW, Yeom GY: Effects of etch-induced damage and contamination on the physical and electrical properties of cobalt silicides. Jpn J Appl Phys 1999, 38: 5788–5791. 10.1143/JJAP.38.5788View Article
- Gamo K: Nanofabrication by FIB. Microelectron Eng 1996, 32: 159–171. 10.1016/0167-9317(96)00003-2View Article
- Spoldi G, Beuer S, Rommel M, Yanev V, Bauer AJ, Ryssel H: Experimental observation of FIB induced lateral damage on silicon samples. Microelectron Eng 2009, 86: 548–551. 10.1016/j.mee.2009.01.003View Article
- Khalfaoui N, Rotaru CC, Bouffard S, Jacquet E, Lebius H, Toulemonde M: Study of swift heavy ion tracks on crystalline quartz surfaces. Nucl Instr Methods Phys Res B 2003, 209: 165–169. 10.1016/S0168-583X(02)02014-1View Article
- Rangelow IW: Scanning proximity probes for nanoscience and nanofabrication. Microelectron Eng 2006, 83: 1449–1455. 10.1016/j.mee.2006.01.199View Article
- Fang TH, Weng CI, Chang JG: Machining characterization of the nano-lithography process using atomic force microscopy. Nanotechnology 2000, 11: 181–187. 10.1088/0957-4484/11/3/308View Article
- Campbell PM, Snow ES, Mcmarr PJ: AFM-based fabrication of Si nanostructures. Physica B 1996, 227: 315–317. 10.1016/0921-4526(96)00429-2View Article
- Matsumoto K, Ishii M, Segawa K, Oka Y, Vartanian BJ, Harris JS: Room temperature operation of a single electron transistor made by the scanning tunneling microscope nanooxidation processfor the TiOx/Ti system. Appl Phys Lett 1996, 68: 34–36. 10.1063/1.116747View Article
- Torii A, Sasaki M, Hane K, Okuma S: A method for determining the spring constant of cantilevers for atomic force microscopy. Meas Sci Technol 1996, 7: 179–184. 10.1088/0957-0233/7/2/010View Article
- Yu BJ, Qian LM, Dong HS, Yu JX, Zhou ZR: Friction-induced hillocks on monocrystalline silicon in atmosphere and in vacuum. Wear 2010, 268: 1095–1102. 10.1016/j.wear.2010.01.007View Article
- Yu BJ, Dong HS, Qian LM, Chen YF, Yu JX, Zhou ZR: Friction-induced nanofabrication on monocrystalline silicon. Nanotechnology 2009, 20: 303–465.
- Chou SY, Keimel C, Gu J: Ultrafast and direct imprint of nanostructures in silicon. Nature 2002, 417: 835–837. 10.1038/nature00792View Article
- Kaneko R, Miyamoto T, Andoh Y, Hamada E: Microwear. Thin Solid Films 1996, 273: 105–111. 10.1016/0040-6090(95)06801-5View Article
- Yu JX, Qian LM, Yu BJ, Zhou ZR: Nanofretting behaviors of monocrystalline silicon (1 0 0) against diamond tips in atmosphere and vacuum. Wear 2009, 267: 322–329. 10.1016/j.wear.2008.11.008View Article
- Miyake S, Kim J: Nanoprocessing of silicon by mechanochemical reaction using atomic force microscopy and additional potassium hydroxide solution etching. Nanotechnology 2005, 16: 149–157. 10.1088/0957-4484/16/1/029View Article
- Johnson KJ: Contact Mechanics. Cambridge, UK. Cambridge University Press; 1985.View Article
- Guzzo PL, Raslan AA, De Mello JDB: Ultrasonic abrasion of quartz crystals. Wear 2003, 255: 67–77. 10.1016/S0043-1648(03)00094-2View Article
- Gercek H: Poisson's ratio values for rocks. Int J Rock Mech Min 2007, 44: 1–13. 10.1016/j.ijrmms.2006.04.011View Article
- Oliver WC, Pharr GM: An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J Mater Res 1992, 7: 1564–1583. 10.1557/JMR.1992.1564View Article
- Franssila S: Introduction to Microfabrication. Chichester, UK. John Wiley & Sons Ltd; 2004.
- Yu JX, Qian LM, Yu BJ, Zhou ZR: Effect of surface hydrophilicity on the nanofretting behavior of Si (100) in atmosphere and vacuum. J Appl Phys 2010, 108: 034314. 10.1063/1.3463306View Article
- Meike A: Considerations for quantitative determination of the role of dislocations in selective dissolution. Earth-Sci Rev 1990, 29: 309–320. 10.1016/0012-8252(90)90045-WView Article
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