Local symmetry distortion induced anomalous thermal conduction in thermoelectric layered oxyselenides

Abstract

Polyhedral distortion, associated closely with the atomic arrangement and interatomic interactions, drives many unique behaviors in solids, such as phase transition and negative thermal expansion. In thermoelectric heteroanionic oxides, the anionic polyhedra are widely present, but their effect on thermal transport is rarely investigated. Here, we report an anomalous thermal conduction induced by local symmetry distortion in layered oxyselenides via solving the Boltzmann transport equation based on first-principles calculations. We found interestingly that lighter BiCuSeO exhibits lower thermal conductivity than heavier BiAgSeO. Due to the different distorted degrees of CuSe4 and AgSe4 tetrahedrons, Cu prefers the in-plane vibration, while Ag has more tendency of out-of-plane vibration. Thus, the heat-carrying phonons dominated by the rattling-like vibration of Cu are significantly suppressed, resulting in lower thermal conductivity of BiCuSeO. This study highlights the importance of polyhedral distortion in regulating thermal conduction in layered heteroanionic materials.