Acoustic-Soft Optical Mode Coupling Leads to Negative Thermal Expansion of GeTe near the Ferroelectric Phase Transition

TL;DR

This paper uses first principles calculations to explain the negative thermal expansion of GeTe near its phase transition, highlighting the role of acoustic-soft optical phonon coupling.

Contribution

It introduces a first principles approach that captures the negative thermal expansion in GeTe by analyzing phonon coupling and elastic constants.

Findings

Negative thermal expansion of GeTe near phase transition accurately reproduced

Coupling between acoustic and soft optical phonons causes negative expansion

Low lattice thermal conductivity linked to phonon coupling

Abstract

GeTe is a well-known ferroelectric and thermoelectric material that undergoes a structural phase transition from a rhombohedral to the rocksalt structure at $\sim 600-700$ 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 each structural parameter in a manner similar to the traditional Gr{\"u}neisen theory, and account for the temperature dependence of elastic constants. We obtain the temperature variation 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.