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A first-principles lattice dynamical study of type-I, type-II, and type-VIII silicon clathrates

Journal of Materials Science volume 51, pages 4538–4548 (2016)Cite this article

Abstract

The pristine crystalline type-I, type-II, and type-VIII silicon clathrates have been studied using state of the art first-principles calculations based on density functional theory and density functional perturbation theory. We apply quasi-harmonic approximation to study structural stability, the possibility of temperature or pressure-driven phase transitions, along with Grüneisen parameters, coefficients of thermal expansion and thermal conductivities to estimate the degree of phonon anharmonicity for selected silicon clathrates. It is shown that a pressure-driven phase transition between type-I and type-II silicon clathrates may occur, and a temperature-driven phase transition between type-I and type-VIII Si clathrates at high temperature is likely. We further show that the relatively high Grüneisen parameters (1.5, 1.65, and 1.29, respectively for Si46-I, Si136-II, Si46-VIII), the existence of negative regions in the thermal expansion coefficient curves and very low thermal conductivities all indicate that the phonon anharmonicity in these silicon clathrates is high.

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Notes

  1. The Birch-Murnaghan equation of state for the energy E as a function of volume V reads E(V) = E 0 + 9/8(BV 0)[(V 0/V)2/3 − 1]2 {1 + [(4 − B′)/2][1 − (V 0/V)2/3]}. E, E 0 , V, V 0, B and B′ are the energy, minimum energy, the volume, volume at the minimum energy, the bulk modulus and its pressure derivative, respectively.

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Acknowledgements

The authors would like to thank the Texas Tech High Performance Computing Center for many hours of computing time.

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Authors and Affiliations

  1. School of Electrical and Computer Engineering, Helmerich Advanced Technology Research Center, Oklahoma State University, 74106, Tulsa, OK, USA

    Payam Norouzzadeh

  2. Department of Physics, Texas Tech University, Lubbock, TX, 79409-1051, USA

    Charles W. Myles

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  1. Payam Norouzzadeh
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  2. Charles W. Myles
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Correspondence to Payam Norouzzadeh.

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Norouzzadeh, P., Myles, C.W. A first-principles lattice dynamical study of type-I, type-II, and type-VIII silicon clathrates. J Mater Sci 51, 4538–4548 (2016). https://doi.org/10.1007/s10853-016-9766-1

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