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Liquid–liquid phase transition in supercooled silicon

Nature Materials volume 2, pages 739–743 (2003)Cite this article

Abstract

Silicon in its liquid and amorphous forms occupies a unique position among amorphous materials. Obviously important in its own right, the amorphous form is structurally close to the group of 4–4, 3–5 and 2–6 amorphous semiconductors that have been found to have interesting pressure-induced semiconductor-to-metal phase transitions1,2. On the other hand, its liquid form has much in common, thermodynamically, with water and other ‘tetrahedral network’ liquids that show density maxima3,4,5,6,7. Proper study of the ‘liquid–amorphous transition’, documented for non-crystalline silicon by both experimental and computer simulation studies8,9,10,11,12,13,14,15,16,17, may therefore also shed light on phase behaviour in these related materials. Here, we provide detailed and unambiguous simulation evidence that the transition in supercooled liquid silicon, in the Stillinger–Weber potential18, is thermodynamically of first order and indeed occurs between two liquid states, as originally predicted by Aptekar10. In addition we present evidence to support the relevance of spinodal divergences near such a transition, and the prediction3 that the transition marks a change in the liquid dynamic character from that of a fragile liquid to that of a strong liquid.

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Figure 1: Coexistence between two amorphous phases of supercooled liquid silicon. Main panel: Plot of enthalpy against temperature, from constant pressure, constant enthalpy simulations as well as constant pressure, constant temperature simulations for the supercooled liquid above and below the liquid–liquid transition.
Figure 2: Diffusivity in the two liquids, and heat capacity in the high-temperature liquid. a, Mean squared displacement for T = 1,055 K obtained from constant pressure, constant temperature simulations, ensuring absence of crystallization as explained in Methods.
Figure 3: Structural change. a, The pair correlation function is shown for three temperatures above and one below the transition (upper set of curves).
Figure 4: Fragile-to-strong transition. Main panel: The intermediate scattering function F(k,t) (see Methods) from simulations of 512 particles, above and below the transition, (T = 1,070 and 1,055 K, respectively.

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Acknowledgements

We thank S. Balasubramanian, G. H. Gilmer, P. H. Poole, F. Sciortino, J. Horbach, R. D. Mountain and W. Kob for useful discussions and comments on the manuscript.

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  1. Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur Campus, 560064, Bangalore, India

    Srikanth Sastry

  2. Department of Chemistry and Biochemistry, Arizona State University, Arizona, 85287-1604, Tempe, USA

    C. Austen Angell

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  1. Srikanth Sastry
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Correspondence to Srikanth Sastry.

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Sastry, S., Austen Angell, C. Liquid–liquid phase transition in supercooled silicon. Nature Mater 2, 739–743 (2003). https://doi.org/10.1038/nmat994

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