Strong acoustic phonon suppression leads to ultralow thermal conductivity and enhanced thermoelectric performance in BaCuGdTe$_3$

Abstract

Excitations and scatterings among the quantized lattice vibrations, i.e., phonons, govern the lattice thermal conductivity ($κ_l$) in crystalline solids. Therefore, effective modulation of $κ_l$ can be achieved through selective manipulation of phonon modes that strongly participate in the heat transport mechanisms. Here, combining accurate first-principles density functional theory calculations and Boltzmann transport theory, we report a layered quaternary chalcogenide semiconductor, BaCuGdTe$_3$, which exhibits unusually low $κ_l$ ($\sim$ 0.14 W/mK at room temperature) despite its ordered crystalline structure. Our analysis reveals that the ultralow $κ_l$ arises mainly from a strong suppression of acoustic phonon modes induced by local distortion, shear vibrations among the layers, and large acoustic-optical avoided-crossing between phonons, which collectively enhances the phonon-scattering rates. Further calculations of the electrical transport properties with explicit consideration of electron-phonon interactions reveal a high thermoelectric figure of merit exceeding unity for this compound at moderate temperature (400-700 K) and carrier concentration $(1\text{--}5 \times 10^{19}\ \text{cm}^{-3})$ ranges. Our theoretical predictions warrant experimental investigations of the intriguing phonon dynamics, thermal transport mechanisms, and thermoelectric properties in this compound. Moreover, insights from our analysis can be used to design and engineer compounds with ultralow $κ_l$.