Ultrastable glasses from in silico vapour deposition

  • A Corrigendum to this article was published on 21 May 2014

Abstract

Glasses are generally prepared by cooling from the liquid phase, and their properties depend on their thermal history. Recent experiments indicate that glasses prepared by vapour deposition onto a substrate can exhibit remarkable stability, and might correspond to equilibrium states that could hitherto be reached only by glasses aged for thousands of years. Here we create ultrastable glasses by means of a computer-simulation process that mimics physical vapour deposition. These stable glasses have, far below the conventional glass-transition temperature, the properties expected for the equilibrium supercooled liquid state, and optimal stability is attained when deposition occurs at the Kauzmann temperature. We also show that the glasses’ extraordinary stability is associated with distinct structural motifs, in particular the abundance of regular Voronoi polyhedra and the relative lack of irregular polyhedra.

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Figure 1: Inherent-structure energy and potential energy of ordinary glasses prepared at different cooling rates and of vapour-deposited glasses prepared at different substrate temperatures.
Figure 2: Effect of heating on the potential energy of ordinary and vapour-deposited glasses.
Figure 3: Boson peak and configurational entropy of ordinary and vapour-deposited glasses.
Figure 4: Structural features of ordinary glasses and vapour-deposited glasses prepared at = 0.3.

Change history

  • 13 May 2014

    We reported the formation of stable binary glass films by vapour deposition. The results were generated on relatively small samples. Simulations of larger systems carried out after the publication of this work have revealed that a significant fraction of the stabilization effect reported can be attributed to composition inhomogeneities that arise near the interfaces of the films. An analysis of these effects is reported in J. Chem. Phys. 139, 144505 (2013). In particular, the extrapolated cooling rates that would be required to generate ordinary glasses with inherent-structure energies comparable to those of vapour-deposited glasses are approximately 2–3 orders of magnitude smaller than the cooling rates used in traditional liquid-cooling simulations. This number is in contrast to the 19 orders-of-magnitude difference inferred from the smaller samples. Configuration files for the larger systems and the corresponding characterizations are available, and can be provided on request. Furthermore, in the Supplementary Information, in Table T1, the values of the energies EIS and <U>, and the Q6 parameter corresponding to ordinary glasses, and in Table T2, the <U> values, have been corrected to reflect the reported densities. Ivan Lyubimov, from the Institute of Molecular Engineering, University of Chicago, performed the calculations that led to this correction.

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Acknowledgements

This work was supported by the National Science Foundation under awards DMR-1234320 and DMR-1121288 (S.S. and J.J.d.P.) and by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under award DE-SC0002161 (M.D.E.). The authors are grateful to L. Yu for helpful discussions.

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S.S. performed the simulations and calculations included in this report. M.D.E. and J.J.d.P. conceived and planned the study. All authors contributed to the preparation of the manuscript.

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Correspondence to Juan J. de Pablo.

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The authors declare no competing financial interests.

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Singh, S., Ediger, M. & de Pablo, J. Ultrastable glasses from in silico vapour deposition. Nature Mater 12, 139–144 (2013). https://doi.org/10.1038/nmat3521

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