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Switching stiction and adhesion of a liquid on a solid

Abstract

When a gecko moves on a ceiling it makes use of adhesion and stiction. Stiction—static friction—is experienced on microscopic and macroscopic scales and is related to adhesion and sliding friction1. Although important for most locomotive processes, the concepts of adhesion, stiction and sliding friction are often only empirically correlated. A more detailed understanding of these concepts will, for example, help to improve the design of increasingly smaller devices such as micro- and nanoelectromechanical switches2. Here we show how stiction and adhesion are related for a liquid drop on a hexagonal boron nitride monolayer on rhodium3, by measuring dynamic contact angles in two distinct states of the solid–liquid interface: a corrugated state in the absence of hydrogen intercalation and an intercalation-induced flat state. Stiction and adhesion can be reversibly switched by applying different electrochemical potentials to the sample, causing atomic hydrogen to be intercalated or not. We ascribe the change in adhesion to a change in lateral electric field of in-plane two-nanometre dipole rings4, because it cannot be explained by the change in surface roughness known from the Wenzel model5. Although the change in adhesion can be calculated for the system we study6, it is not yet possible to determine the stiction at such a solid–liquid interface using ab initio methods. The inorganic hybrid of hexagonal boron nitride and rhodium is very stable and represents a new class of switchable surfaces with the potential for application in the study of adhesion, friction and lubrication.

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Figure 1: Voltammetry and electrochemical scanning tunnelling microscopy.
Figure 2: Deuterium thermal desorption spectra.
Figure 3: Dynamic contact angle measurements.
Figure 4: Wetting angle hysteresis and stiction.

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References

  1. Persson, B. N. J. Sliding Friction (Springer, 1998)

  2. Wagner, T. J. W. & Vella, D. Switch on, switch off: stiction in nanoelectromechanical switches. Nanotechnology 24, 275501 (2013)

    Article  Google Scholar 

  3. Corso, M. et al. Boron nitride nanomesh. Science 303, 217–220 (2004)

    Article  CAS  ADS  Google Scholar 

  4. Dil, H. et al. Surface trapping of atoms and molecules with dipole rings. Science 319, 1824–1826 (2008)

    Article  CAS  ADS  Google Scholar 

  5. Wenzel, R. N. Surface roughness and contact angle. J. Phys. Chem. 53, 1466–1467 (1949)

    Article  CAS  Google Scholar 

  6. Golze, D., Hutter, J. & Iannuzzi, M. Wetting of water on hexagonal boron nitride@Rh(111): a QM/MM model based on atomic charges derived for nanostructured substrates. Phys. Chem. Chem. Phys. 17, 14307–14316 (2015)

    Article  CAS  Google Scholar 

  7. Ternes, M., Lutz, C. P., Hirjibehedin, C. F., Giessibl, F. J. & Heinrich, A. J. The force needed to move an atom on a surface. Science 319, 1066–1069 (2008)

    Article  CAS  ADS  Google Scholar 

  8. Krim, J., Solina, D. H. & Chiarello, R. Nanotribology of a Kr monolayer: a quartz crystal microbalance study of atomic-scale friction. Phys. Rev. Lett. 66, 181–184 (1991)

    Article  CAS  ADS  Google Scholar 

  9. Ehrlich, G. & Hudda, F. Atomic view of surface self-diffusion: tungsten on tungsten. J. Chem. Phys. 44, 1039–1049 (1966)

    Article  CAS  ADS  Google Scholar 

  10. Evans, M. G. & Polanyi, M. Inertia and driving force of chemical reactions. Trans. Faraday Soc. 34, 11–24 (1938)

    Article  CAS  Google Scholar 

  11. Zhang, Q., Qi, Y., Hector, L. G. Jr, Cagin, T. & Goddard, W. A. III. Origin of static friction and its relationship to adhesion at the atomic scale. Phys. Rev. B 75, 144114 (2007)

    Article  ADS  Google Scholar 

  12. Ichimura, K., Oh, S.-K. & Nakagawa, M. Light-driven motion of liquids on a photoresponsive surface. Science 288, 1624–1626 (2000)

    Article  CAS  ADS  Google Scholar 

  13. Sun, T. et al. Reversible switching between superhydrophilicity and superhydrophobicity. Angew. Chem. Int. Ed. 43, 357–360 (2004)

    Article  CAS  Google Scholar 

  14. Lahann, J. et al. A reversibly switching surface. Science 299, 371–374 (2003)

    Article  CAS  ADS  Google Scholar 

  15. Berner, S. et al. Boron nitride nanomesh: functionality from a corrugated monolayer. Angew. Chem. Int. Ed. 46, 5115–5119 (2007)

    Article  CAS  Google Scholar 

  16. Widmer, R. et al. Electrolytic in situ STM investigation of h-BN-nanomesh. Electrochem. Commun. 9, 2484–2488 (2007)

    Article  CAS  Google Scholar 

  17. Brugger, T. et al. Nanotexture switching of single-layer hexagonal boron nitride on rhodium by intercalation of hydrogen atoms. Angew. Chem. Int. Ed. 49, 6120–6124 (2010)

    Article  CAS  Google Scholar 

  18. Willman, K. W. & Murray, R. W. Contact angle between water and a poly(vinylferrocene) film on a potential-controlled platinum electrode. Anal. Chem. 55, 1139–1142 (1983)

    Article  CAS  Google Scholar 

  19. Sung, Y. E., Thomas, S. & Wieckowski, A. Characterization of the Rh(111) electrode by CEELS, AES, LEED, and voltammetry. Adsorption of (bi)sulfate, perchlorate, and carbon monoxide. J. Phys. Chem. 99, 13513–13521 (1995)

    Article  CAS  Google Scholar 

  20. Colonell, J. I., Curtiss, T. J. & Sibener, S. J. Coverage dependence of the kinetics for H2 desorption from Rh(111). Surf. Sci. 366, 19–28 (1996)

    Article  CAS  ADS  Google Scholar 

  21. Hu, S. et al. Proton transport through one-atom-thick crystals. Nature 516, 227–230 (2014)

    Article  CAS  ADS  Google Scholar 

  22. Marx, D., Tuckerman, M. E., Hutter, J. & Parrinello, M. The nature of the hydrated excess proton in water. Nature 397, 601–604 (1999)

    Article  CAS  ADS  Google Scholar 

  23. de Gennes, P. G. Wetting: statics and dynamics. Rev. Mod. Phys. 57, 827–863 (1985)

    Article  MathSciNet  CAS  ADS  Google Scholar 

  24. Kwok, D. Y. & Neumann, A. W. Contact angle measurement and contact angle interpretation. Adv. Colloid Interface Sci. 81, 167–249 (1999)

    Article  CAS  Google Scholar 

  25. Amirfazli, A., Hanig, S., Müller, A. & Neumann, A. W. Measurements of line tension for solid–liquid–vapor systems using drop size dependence of contact angles and its correlation with solid–liquid interfacial tension. Langmuir 16, 2024–2031 (2000)

    Article  CAS  Google Scholar 

  26. Schneemilch, M., Welters, W. J. J., Hayes, R. A. & Ralston, J. Electrically induced changes in dynamic wettability. Langmuir 16, 2924–2927 (2000)

    Article  CAS  Google Scholar 

  27. Manukyan, G., Oh, J. M., van den Ende, D., Lammertink, R. G. H. & Mugele, F. Electrical switching of wetting states on superhydrophobic surfaces: a route towards reversible Cassie-to-Wenzel transitions. Phys. Rev. Lett. 106, 014501 (2011)

    Article  CAS  ADS  Google Scholar 

  28. Schrader, M. E. Young–Dupré revisited. Langmuir 11, 3585–3589 (1995)

    Article  CAS  Google Scholar 

  29. Iannuzzi, M. et al. Site-selective adsorption of phthalocyanine on h-BN/Rh(111) nanomesh. Phys. Chem. Chem. Phys. 16, 12374–12384 (2014)

    Article  CAS  Google Scholar 

  30. Ma, H. et al. Chiral distortion of confined ice oligomers (n = 5,6). Langmuir 28, 15246–15250 (2012)

    Article  CAS  Google Scholar 

  31. Ding, Y., Iannuzzi, M. & Hutter, J. Investigation of boron nitride nanomesh interacting with water. J. Phys. Chem. C 115, 13685–13692 (2011)

    Article  CAS  Google Scholar 

  32. Holzschuh, E., Fritschi, M. & Kündig, W. Measurement of the electron neutrino mass from tritium β-decay. Phys. Lett. B 287, 381–388 (1992)

    Article  ADS  Google Scholar 

  33. Hemmi, A. et al. High quality single atomic layer deposition of hexagonal boron nitride on single crystalline Rh(111) four-inch wafers. Rev. Sci. Instrum. 85, 035101 (2014)

    Article  CAS  ADS  Google Scholar 

  34. King, S. W., Nemanich, R. J. & Davis, R. F. Cleaning of pyrolytic hexagonal boron nitride surfaces. Surf. Interface Anal. 47, 798–803 (2015)

    Article  CAS  Google Scholar 

  35. Cun, H., Iannuzzi, M., Hemmi, A., Osterwalder, J. & Greber, T. Two-nanometer voids in single-layer hexagonal boron nitride: formation via the “can-opener” effect and annihilation by self-healing. ACS Nano 8, 7423–7431 (2014)

    Article  CAS  Google Scholar 

  36. Hansen, W. N. & Kolb, D. M. The work function of emersed electrodes. J. Electroanal. Chem. 100, 493–500 (1979)

    Article  CAS  Google Scholar 

  37. Koper, M. T. M. Blank voltammetry of hexagonal surfaces of Pt-group metal electrodes: comparison to density functional theory calculations and ultra-high vacuum experiments on water dissociation. Electrochim. Acta 56, 10645–10651 (2011)

    Article  CAS  Google Scholar 

  38. Jerkiewicz, G. & Zolfaghari, A. Determination of the energy of the metal–underpotential-deposited hydrogen bond for rhodium electrodes. J. Phys. Chem. 100, 8454–8461 (1996)

    Article  CAS  Google Scholar 

  39. Zolfaghari, A., Chayer, M. & Jerkiewicz, G. Energetics of the underpotential deposition of hydrogen on platinum electrodes. I. Absence of coadsorbed species. J. Electrochem. Soc. 144, 3034–3041 (1997)

    Article  CAS  ADS  Google Scholar 

  40. Łosiewicz, B., Jurczakowski, R. & Lasia, A. Kinetics of hydrogen underpotential deposition at polycrystalline rhodium in acidic solutions. Electrochim. Acta 56, 5746–5753 (2011)

    Article  Google Scholar 

Download references

Acknowledgements

We acknowledge financial support by the Swiss National Science Foundation within the funding instrument ‘Sinergia’. S.F.L.M. acknowledges the receipt of an FP7 Marie Curie European reintegration grant, ERC grant OxideSurfaces and, together with S.D.F., support by FWO–Vlaanderen. We thank M. Schmid for help with the depiction of the STM images, G. Schütz for discussions and A. P. Seitsonen for the artwork in Fig. 1g.

Author information

Authors and Affiliations

Authors

Contributions

T.G. conceived the project together with S.F.L.M., who designed and performed the electrochemical experiments, in situ STM and in situ contact angle measurements. A.H. prepared the nanomesh samples, analysed contact angle data and performed the TDS measurements. S.M. built the contact angle apparatus. O.G. drew our attention to dynamic contact angle measurements. S.D.F. and J.O. managed the Sinergia project. All authors contributed to discussions. S.F.L.M., A.H. and T.G. prepared the manuscript.

Corresponding authors

Correspondence to Stijn F. L. Mertens or Thomas Greber.

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Competing interests

The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 Thermal desorption spectroscopy.

a, h-BN/Rh(111) thin-film sample and sample holder ready for the desorption experiment in the ultrahigh-vacuum chamber. b, Thermal desorption experiment with temperature and power data shown in the top panel and pressure data in the bottom panel. The purple data are pyrometer readings, which were calibrated to a previous thermocouple measurement using a Rh crystal. The simulated temperature is a solution of equations (1) and (2) with the applied power and a starting temperature of 25 °C as input variables.

Extended Data Figure 2 Electrochemical STM during hydrogen intercalation.

The substrate potential during scanning (image scanned from bottom to top) was switched from E1 = 0 V (deintercalated, yellow arrow) to E2 = −0.25 V (intercalated, light blue arrow) at about one-fifth of the way from the lower edge of the STM image. On the timescale of imaging, intercalation-induced flattening of the surface is instantaneous, in sharp contrast to deintercalation (compare with Fig. 1e). Image size, 66 nm × 66 nm; tunnelling current, 0.1 nA; tip potential fixed at −0.45 V.

Supplementary information

Advancing, followed by receding electrolyte drop on h-BN/Rh(111), at an applied substrate potential E = +0.1 V

Advancing, followed by receding electrolyte drop on h-BN/Rh(111), at an applied substrate potential E = +0.1 V, where the nanomesh occurs in its normal corrugated state. The video shows all images captured between t = 68 s and t = 80 s in Figure 3a. (MOV 4472 kb)

Advancing, followed by receding electrolyte drop on h-BN/Rh(111), at an applied substrate potential E = –0.35 V

Advancing, followed by receding electrolyte drop on h-BN/Rh(111), at an applied substrate potential E = –0.35 V, where hydrogen intercalation has caused flattening of the nanomesh. The video shows all images captured between between t = 95 s and t = 115 s in Figure 3b. (MOV 7657 kb)

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Mertens, S., Hemmi, A., Muff, S. et al. Switching stiction and adhesion of a liquid on a solid. Nature 534, 676–679 (2016). https://doi.org/10.1038/nature18275

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