The origin of the lattice thermal conductivity enhancement at the ferroelectric phase transition in GeTe

The proximity to structural phase transitions in IV-VI thermoelectric materials is one of the main reasons for their large phonon anharmonicity and intrinsically low lattice thermal conductivity $\kappa$. However, the $\kappa$ of GeTe increases at the ferroelectric phase transition near $700$ K. Using first-principles calculations with the temperature dependent effective potential method, we show that this rise in $\kappa$ is the consequence of negative thermal expansion in the rhombohedral phase and increase in the phonon lifetimes in the high-symmetry phase. Negative thermal expansion increases phonon group velocities, which counteracts enhanced anharmonicity of phonon modes and boosts $\kappa$ close to the phase transition in the rhombohedral phase. A drastic decrease in the anharmonic force constants in the cubic phase increases the phonon lifetimes and $\kappa$. Strong anharmonicity near the phase transition induces non-Lorentzian shapes of the phonon power spectra. To account for these effects, we implement a novel method of calculating $\kappa$ based on the Green-Kubo approach and find that the Boltzmann transport equation underestimates $\kappa$ near the phase transition. Our findings elucidate the influence of structural phase transitions on $\kappa$ and provide guidance for design of better thermoelectric materials.

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