Coupling between acoustic and soft transverse optical phonons leads to negative thermal expansion of GeTe near the ferroelectric phase transition

Abstract

GeTe is a well-known ferroelectric and thermoelectric material that undergoes a structural phase transition from a rhombohedral to the rocksalt structure at ∼600 – 700 K. We present a first-principles approach to calculate the thermal expansion of GeTe in the rhombohedral phase up to the Curie temperature. We find the minimum of the Helmholtz free energy with respect to the structural parameters, including the internal atomic displacement, in a manner similar to the traditional Grüneisen theory, explicitly accounting for the variation of the static elastic energy with respect to all structural parameters. We obtain the temperature dependence of the structural parameters of rhombohedral GeTe in very good agreement with experiments. In particular, we correctly reproduce a negative volumetric thermal expansion of GeTe near the phase transition. We show that the negative thermal expansion is induced by the coupling between acoustic and soft transverse optical phonons, which is also responsible for the low lattice thermal conductivity of GeTe.