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Ultrastable glasses from in silico vapour deposition

Nature Materials volume 12, pages 139–144 (2013)Cite this article

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A Corrigendum to this article was published on 21 May 2014

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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.

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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.

References

  1. Angell, C. A. Formation of glasses from liquids and biopolymers. Science 267, 1924–1935 (1995).

    Article  CAS  Google Scholar 

  2. Swallen, S. F. et al. Organic glasses with exceptional thermodynamic and kinetic stability. Science 315, 353–356 (2007).

    Article  CAS  Google Scholar 

  3. Weber, T. A. & Stillinger, F. H. Local order and structural transitions in amorphous metal-metalloid alloys. Phys. Rev. B 31, 1954–1963 (1985).

    Article  CAS  Google Scholar 

  4. Kob, W. & Andersen, H. C. Testing mode-coupling theory for a supercooled binary Lennard-Jones mixture—the van Hove correlation-function. Phys. Rev. E 51, 4626–4641 (1995).

    Article  CAS  Google Scholar 

  5. Sastry, S., Debenedetti, P. G. & Stillinger, F. H. Signatures of distinct dynamical regimes in the energy landscape of a glass-forming liquid. Nature 393, 554–557 (1998).

    Article  CAS  Google Scholar 

  6. Berthier, L. et al. Direct experimental evidence of a growing length scale accompanying the glass transition. Science 310, 1797–1800 (2005).

    Article  CAS  Google Scholar 

  7. Isner, B. A. & Lacks, D. J. Generic rugged landscapes under strain and the possibility of rejuvenation in glasses. Phys. Rev. Lett. 96, 025506 (2006).

    Article  Google Scholar 

  8. Jack, R. L., Hedges, L. O., Garrahan, J. P. & Chandler, D. Preparation and relaxation of very stable glassy states of a simulated liquid. Phys. Rev. Lett. 85, 275702 (2011).

    Article  Google Scholar 

  9. Kob, W., Roldan-Vargas, S. & Berthier, L. Non-monotonic temperature evolution of dynamic correlations in glass-forming liquids. Nature Phys. 8, 164–167 (2012).

    Article  CAS  Google Scholar 

  10. Stillinger, F. H. A topographic view of supercooled liquids and glass-formation. Science 267, 1935–1939 (1995).

    Article  CAS  Google Scholar 

  11. Sciortino, F. Potential energy landscape description of supercooled liquids and glasses. J. Stat. Mech. P05015 (2005).

  12. Ramos, S. L. L. M., Oguni, M., Ishii, K. & Nakayama, H. Character of devitrification, viewed from enthalpic paths, of the vapor-deposited ethylbenzene glasses. J. Phys. Chem. B 115, 14327–14332 (2011).

    Article  CAS  Google Scholar 

  13. Leon-Gutierrez, E. et al. In situ nanocalorimetry of thin glassy organic films. J. Chem. Phys. 129, 181101 (2008).

    Article  CAS  Google Scholar 

  14. Jiang, H. & Baram, J. Estimation of the glass transition temperature in metallic glasses. Mater. Sci. Eng. A 208, 232–238 (1996).

    Article  Google Scholar 

  15. Fakhraai, Z., Still, T., Fytas, G. & Ediger, M. D. Structural variations of an organic glassformer vapor-deposited onto a temperature gradient stage. J. Chem. Phys. Lett. 2, 423–427 (2011).

    Article  CAS  Google Scholar 

  16. Dawson, K. et al. Highly stable vapor-deposited glasses of four tris-naphthylbenzene isomers. J. Phys. Chem. Lett. 2, 2683–2687 (2011).

    Article  CAS  Google Scholar 

  17. Phillips, W. A., Buchenau, U., Nucker, N., Dianoux, A. J. & Petry, W. Dynamics of glassy and liquid selenium. Phys. Rev. Lett. 63, 2381–2384 (1989).

    Article  CAS  Google Scholar 

  18. Grigera, T. S., Martin-Mayor, V., Parisi, G. & Verrocchio, P. Phonon interpretation of the ‘boson peak’ in supercooled liquids. Nature 422, 289–292 (2003).

    Article  CAS  Google Scholar 

  19. Sastry, S. Liquid limits: Glass transition and liquid-gas spinodal boundaries of metastable liquids. Phys. Rev. Lett. 85, 590–593 (2000).

    Article  CAS  Google Scholar 

  20. Sciortino, F., Kob, W. & Tartaglia, P. Thermodynamics of supercooled liquids in the inherent-structure formalism: A case study. J. Phys. Condens. Matter 12, 6525–6534 (2000).

    Article  CAS  Google Scholar 

  21. Steinhardt, P. J., Nelson, D. R. & Ronchetti, M. Bond-orientational order in liquids and glasses. Phys. Rev. B 28, 784–805 (1983).

    Article  CAS  Google Scholar 

  22. Sheng, H. W., Luo, W. K., Alamgir, F. M., Bai, J. M. & Ma, E. Atomic packing and short-to-medium-range order in metallic glasses. Nature 439, 419–425 (2006).

    Article  CAS  Google Scholar 

  23. Cheng, Y., Cao, A., Sheng, H. & Ma, E. Local order influences initiation of plastic flow in metallic glass: Effects of alloy composition and sample cooling history. Acta Mater. 56, 5263–5275 (2008).

    Article  CAS  Google Scholar 

  24. Coslovich, D. Locally preferred structures and many-body static correlations in viscous liquids. Phys. Rev. E 83, 051505 (2011).

    Article  Google Scholar 

  25. Chen, K. & Schweizer, K. S. Molecular theory of physical aging in polymer glasses. Phys. Rev. Lett. 98, 167802 (2007).

    Article  Google Scholar 

  26. Dawson, K. J., Kearns, K. L., Yu, L., Steffen, W. & Ediger, M. D. Physical vapor deposition as a route to hidden amorphous states. Proc. Natl Acad. Sci. USA 106, 15165–15170 (2009).

    Article  CAS  Google Scholar 

  27. Dawson, K. J., Zhu, L., Yu, L. & Ediger, M. D. Anisotropic structure and transformation kinetics of vapor-deposited indomethacin glasses. J. Phys. Chem. B 115, 455–463 (2011).

    Article  CAS  Google Scholar 

  28. Singh, S. & de Pablo, J. J. A molecular view of vapor deposited glasses. J. Chem. Phys. 134, 194903 (2011).

    Article  Google Scholar 

  29. Martyna, G. J., Klein, M. L. & Tuckerman, M. Nose–Hoover chains—the canonical ensemble via continuous dynamics. J. Chem. Phys. 97, 2635–2643 (1992).

    Article  Google Scholar 

  30. Plimpton, S. Fast parallel algorithms for short-range molecular-dynamics. J. Comput. Phys. 117, 1–19 (1995).

    Article  CAS  Google Scholar 

  31. Colucci, D. et al. Isochoric and isobaric glass formation: Similarities and differences. J. Polym. Sci. 35, 1561–1573 (1997).

    Article  CAS  Google Scholar 

  32. Bitzek, E., Koskinen, P., Gaehler, F., Moseler, M. & Gumbsch, P. Structural relaxation made simple. Phys. Rev. Lett. 97, 170201 (2006).

    Article  Google Scholar 

  33. Gurevich, V. L., Parshin, D. A. & Schober, H. R. Anharmonicity, vibrational instability, and the boson peak in glasses. Phys. Rev. B 67, 094203 (2003).

    Article  Google Scholar 

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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.

Author information

Authors and Affiliations

  1. Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA

    Sadanand Singh & Juan J. de Pablo

  2. Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA

    M. D. Ediger

  3. Institute of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA

    Juan J. de Pablo

  4. Argonne National Laboratory, 9700 South Cass Avenue, Building 223, Argonne, Illinois 60439, USA

    Juan J. de Pablo

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  1. Sadanand Singh
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Contributions

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.

Corresponding author

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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