Optical-Phonon-Enabled Large Lattice Thermal Conductivity Anisotropy in Hexagonal Perovskites Cs$BX_3$ ($B$ = Mg, Cd; $X$ = Cl, Br, I)

Abstract

Materials exhibiting strongly anisotropic lattice thermal conductivity are desirable for thermal-management applications, yet such behavior is commonly associated with layered or quasi-one-dimensional van der Waals crystals and highly anisotropic elastic properties. Here, we investigate lattice thermal transport in the hexagonal perovskites Cs$BX_3$ ($B=$ Mg, Cd; $X=$ Cl, Br, I) using first-principles calculations. At 300~K, the calculated in-plane and out-of-plane lattice thermal conductivities range from 0.13--0.83 and 0.34--6.26~Wm$^{-1}$K$^{-1}$, respectively, corresponding to anisotropy ratios of 2.6--7.5. This pronounced anisotropy is remarkable given the relatively modest elastic anisotropy, characterized by $C_{33}/C_{11}$ = 0.994--1.842. Our analysis reveals that medium-frequency optical phonons provide an efficient out-of-plane heat-transport channel, contrary to the conventional picture in which heat transport is dominated by acoustic phonons. These findings identify face-sharing octahedral frameworks as a promising platform for engineering strong thermal-conductivity anisotropy in mechanically near-isotropic, non--van der Waals crystals.