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Atomically controlled electrochemical nucleation at superionic solid electrolyte surfaces

Nature Materials volume 11, pages 530–535 (2012)Cite this article

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Abstract

Electrochemical equilibrium and the transfer of mass and charge through interfaces at the atomic scale are of fundamental importance for the microscopic understanding of elementary physicochemical processes. Approaching atomic dimensions, phase instabilities and instrumentation limits restrict the resolution. Here we show an ultimate lateral, mass and charge resolution during electrochemical Ag phase formation at the surface of RbAg4I5 superionic conductor thin films. We found that a small amount of electron donors in the solid electrolyte enables scanning tunnelling microscope measurements and atomically resolved imaging. We demonstrate that Ag critical nucleus formation is rate limiting. The Gibbs energy of this process takes discrete values and the number of atoms of the critical nucleus remains constant over a large range of applied potentials. Our approach is crucial to elucidate the mechanism of atomic switches and highlights the possibility of extending this method to a variety of other electrochemical systems.

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Figure 1: Schematic presentation of the distribution of the electrochemical (), chemical (μe) and electrical (φ) potentials (related by ) at three boundary situations.
Figure 2: STM imaging of RbAg4I5 surfaces.
Figure 3: Current–time dependence at an applied voltage of −100 mV.
Figure 4: Voltage and temperature dependence of the switching time.
Figure 5: STM observations of Ag clusters formation and stability.

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References

  1. Maier, J. Nanoionics: Ion transport and electrochemical storage in confined systems. Nature Mater. 4, 805–815 (2005).

    Article  CAS  Google Scholar 

  2. Waser, R. (ed.) Nanotechnology—Volume 3, Information Technology (Wiley, 2008).

  3. Valov, I., Waser, R., Jameson, J. R. & Kozicki, M. N. Electrochemical metallization memories-fundamentals, applications, prospects. Nanotechnology 22, 254003 (2011).

    Article  Google Scholar 

  4. Waser, R. & Aono, M. Nanoionics-based resistive switching memories. Nature Mater. 6, 833–840 (2007).

    Article  CAS  Google Scholar 

  5. Ohno, T. et al. Short-term plasticity and long-term potentiation mimicked in single inorganic synapses. Nature Mater. 10, 591–595 (2011).

    Article  CAS  Google Scholar 

  6. Terabe, K., Hasegawa, T., Nakayama, T. & Aono, M. Quantized conductance atomic switch. Nature 433, 47–50 (2005).

    Article  CAS  Google Scholar 

  7. Tamura, T. et al. Material dependence of switching speed of atomic switches made from silver sulfide and from copper sulfide. J. Phys. Conf. Ser. 61, 1157–1161 (2007).

    Article  CAS  Google Scholar 

  8. Morales-Masis, M., van der Molen, S. J., Hasegawa, T. & van Ruitenbeek, J. M. Bulk and surface nucleation processes in Ag2S conductance switches. Phys. Rev. B 84, 115310 (2011).

    Article  Google Scholar 

  9. Nayak, A., Tsuruoka, T., Terabe, K., Hasegawa, T. & Aono, M. Switching kinetics of a Cu2S-based gap-type atomic switch. Nanotechnology 22, 235201 (2011).

    Article  Google Scholar 

  10. Nayak, A. et al. Rate-limiting processes determining the switching time in a Ag2S atomic switch. J. Phys. Chem. Lett. 1, 604–608 (2010).

    Article  CAS  Google Scholar 

  11. Milchev, A., Stoyanov, S. & Kaischev, R. Atomistic theory of electrolytic nucleation: I. Thin Solid Films 22, 255–265 (1974).

    Article  CAS  Google Scholar 

  12. Budevski, E., Staikov, G. & Lorenz, W. J. Electrochemical Phase Formation and Growth (Wiley, 1996).

    Book  Google Scholar 

  13. Milchev, A. Electrocrystallization: Fundamentals of Nucleation and Growth (Kluwer Academic, 2002).

    Google Scholar 

  14. Hebb, M. H. Electrical conductivity of silver sulfide. J. Chem. Phys. 20, 185–190 (1952).

    Article  CAS  Google Scholar 

  15. Wagner, C. Proc. 7th Meet. Int. Comm. On Electrochem. Thermodynam. Kinet. (Butterworths, 1957).

    Google Scholar 

  16. Delahay, P. Double Layer and Electrode Kinetics (Wiley, 1965).

    Google Scholar 

  17. Butler, J. A kinetic theory of reversible oxidation potentials at inert electrodes. Trans. Faraday Soc. 19, 734–739 (1924).

    Article  Google Scholar 

  18. Erdey-Gruz, T. & Volmer, M. Zur Theorie der Wasserstoffueberspannung. Z. Phys. Chem-Leipzig 150A, 203–213 (1930).

    Google Scholar 

  19. Pinkowski, A., Chierchie, T. & Lorenz, W. Low-temperature ion conductivity of RbAg4I5 . J. Electroanal. Chem. 285, 241–248 (1990).

    Article  CAS  Google Scholar 

  20. Dovesi, R. et al. CRYSTAL09 User’s Manual, University of Torino (2010).

  21. Bredow, T. & Gerson, A.R. Effect of exchange and correlation on bulk properties of MgO, NiO, and CoO. Phys. Rev. B 61, 5194–5201 (2000).

    Article  CAS  Google Scholar 

  22. Leininger, T. et al. The accuracy of the pseudopotential approximation: Non-frozen-core effects for spectroscopic constants of alkali fluorides XF (X=K, Rb, Cs). Chem. Phys. Lett. 255, 274–280 (1996).

    Article  CAS  Google Scholar 

  23. Andrae, D., Haeussermann, U., Dolg, M., Stoll, H. & Preuss, H. Energy-adjusted ab initio pseudopotentials for the 2nd and 3rd row transition elements. Theor. Chim. Acta 77, 123–141 (1990).

    Article  CAS  Google Scholar 

  24. Peterson, K. A., Shepler, B. C., Figgen, D. & Stoll, H. On the spectroscopic and thermochemical properties of ClO, BrO, IO, and their anions. J. Phys. Chem. A 110, 13877–13890 (2006).

    Article  CAS  Google Scholar 

  25. Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys. Chem. Chem. Phys. 7, 3297–3312 (2005).

    Article  CAS  Google Scholar 

  26. Geller, S. Crystal structure of solid electrolyte RbAg4I5 . Science 157, 310–311 (1967).

    Article  CAS  Google Scholar 

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Acknowledgements

The authors would like to thank the German Research Foundation (DFG) and the Japan Science and Technology Agency (JST) for the financial support of the projects W A908/22-1 in Germany and that in Japan. I.S. was supported by the ‘Studienstiftung des deutschen Volkes’. The assistance of T. Pössinger with the graphical layout is gratefully acknowledged.

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Authors and Affiliations

  1. Research Centre Juelich, Peter Gruenberg Institute, Electronic Materials, 52425 Juelich, Germany

    Ilia Valov, Georgi Staikov & Rainer Waser

  2. IWE2 & JARA-FIT, RWTH Aachen University, 52056 Aachen, Germany

    Ina Sapezanskaia & Rainer Waser

  3. International Center for Materials Nanoarchitectonics (WPI—MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, Japan

    Alpana Nayak, Tohru Tsuruoka, Tsuyoshi Hasegawa & Masakazu Aono

  4. Institute of Theoretical Chemistry, University of Bonn, 53115 Bonn, Germany

    Thomas Bredow

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  1. Ilia Valov
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Contributions

I.V. conceived the idea, supervised the measurements, performed the data interpretation and wrote the manuscript. I.S. prepared the samples, performed the measurements and the data evaluation, and contributed to the interpretation. A.N. and T.T. supported the STM measurements and contributed to the interpretation. T.B. performed the DFT calculations, T.H. supervised the STM measurements and contributed to the interpretation. G.S. contributed to the interpretation, M.A and R.W. contributed to the concept of the study and supervised the research. All authors discussed the results and implications at all stages and contributed to the improvement of the manuscript text.

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Correspondence to Ilia Valov.

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The authors declare no competing financial interests.

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Valov, I., Sapezanskaia, I., Nayak, A. et al. Atomically controlled electrochemical nucleation at superionic solid electrolyte surfaces. Nature Mater 11, 530–535 (2012). https://doi.org/10.1038/nmat3307

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