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Surface-induced crystallization in supercooled tetrahedral liquids

Nature Materials volume 8, pages 726–730 (2009)Cite this article

Abstract

Surfaces have long been known to have an intricate role in solid–liquid phase transformations. Whereas melting is often observed to originate at surfaces, freezing usually starts in the bulk, and only a few systems have been reported to exhibit signatures of surface-induced crystallization1. These include assembly of chain-like molecules2, some liquid metals and alloys3,4,5 and silicate glasses6,7. Here, we report direct computational evidence of surface-induced nucleation in supercooled liquid silicon and germanium, and we illustrate the crucial role of free surfaces in the freezing process of tetrahedral liquids exhibiting a negative slope of their melting lines (dT/dP|coexist<0). Our molecular dynamics simulations show that the presence of free surfaces may enhance the nucleation rates by several orders of magnitude with respect to those found in the bulk. Our findings provide insight, at the atomistic level, into the nucleation mechanism of widely used semiconductors, and support the hypothesis of surface-induced crystallization in other tetrahedrally coordinated systems, in particular water in the atmosphere.

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Figure 1: Computed nucleation rates in liquid Si and Ge.
Figure 2: Growth of Si crystallites at 0.95 Tm.
Figure 3: Densities of liquid and diamond cubic silicon modelled by the Tersoff potential as functions of temperature near the melting point Tm.
Figure 4: Effect of p on the homogeneous nucleation rate in the bulk liquid at 0.95 Tm.

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Acknowledgements

We gratefully thank D. C. Chrzan, A. F. Voter and M. Parrinello for fruitful discussions. This work was supported by DOE/BES (contract number DE-FG02-06ER46262).

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Authors and Affiliations

  1. Department of Chemistry, University of California, Davis, California 95616, USA

    Tianshu Li, Davide Donadio & Giulia Galli

  2. Theory Department, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, D14195 Berlin-Dahlem, Germany

    Luca M. Ghiringhelli

Authors
  1. Tianshu Li
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  2. Davide Donadio
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  4. Giulia Galli
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Contributions

T.L., D.D. and G.G. designed the research, interpreted results and wrote the paper; T.L. and D.D. designed and implemented the method and analysed results; T.L. carried out calculations; L.M.G. discussed initial design and implementation of the research.

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Correspondence to Tianshu Li.

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Li, T., Donadio, D., Ghiringhelli, L. et al. Surface-induced crystallization in supercooled tetrahedral liquids. Nature Mater 8, 726–730 (2009). https://doi.org/10.1038/nmat2508

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