High Thermoelectric Performance via Stacking-Controlled Symmetry Breaking in Layered XZnBi (X = Rb, Cs) Zintl Materials

Abstract

High thermoelectric efficiency requires high Seebeck coefficient, high electrical conductivity, and low thermal conductivity. However, strategies that suppress thermal conductivity often simultaneously degrade electrical conductivity, making effective electrical-thermal decoupling highly challenging. Here, we show that atomic-layer stacking order change in XZnBi (X = Rb, Cs) provides an efficient route to achieve such decoupling. Even though electronic transport coefficients and relaxation times remain largely insensitive to stacking order due to preserved Fermi-surface topology, the lattice thermal conductivity exhibits a strong stacking dependence, with AB stacking significantly suppressing it below 1 Wm${}^{-1}$K${}^{-1}$ at temperatures above 300 K. The stacking transition from AA to AB breaks structural symmetries. It increases the three-phonon phase space and available scattering channel, substantially suppressing phonon transport by about 50$\%$ in both materials. As a result, the AB-stacked phases yield high ZT values of 1.96 (1.69) in n-type CsZnBi (RbZnBi) at 900 K, which is about 40$\%$ (30$\%$) higher than AA stacking. These findings establish the XZnBi family as promising thermoelectric candidates and highlight stacking-order controlled phonon transport as a robust strategy for advancing thermoelectric material design.

38 pages. In this new version, the electcron relaxtion time calculations of EPW is well integrated with transport coefficient. Be sure to refer to this version while previous ones were withdrawn