Impact of Temperature-Dependent Rattling Phonons on Lattice Dynamics and Thermal Transport in Ag${}_6$Ge${}_{10}$P${}_{12}$

Abstract

Crystalline compounds exhibiting low-frequency rattling phonons constitute an important class of high-performance thermoelectrics owning to their intrinsically very low lattice thermal conductivity (${\kappa }_l$). Theoretical approach that is capable of revealing the physical origin and accurately predicting ${\kappa }_l$ is of particular interest, which, however, still remains an outstanding challenge. In this study, we perform a case study of lattice dynamics and thermal transport properties of Ag${}_6$Ge${}_{10}$P${}_{12}$, which has recently been identified as a high-performance thermoelectric phosphide due to low ${\kappa }_l$, arising from rattling vibrations associated with Ag${}_6$ clusters. Analysis within a first-principles-based lattice-dynamics framework based on self-consistent phonon theory reveals a strong temperature dependence of rattling phonons due to high-order anharmonic interactions. Anharmonic hardening of the rattling optical modes has a strong effect on the lifetimes of heat-carrying acoustic phonons by decreasing the rate of three-phonon combination processes. This mechanism results in a significant increase in ${\kappa }_l$ and changes its temperature dependence to $1/T^{0.64}$.