First-principles study of anisotropic thermoelectric transport properties of IV-VI semiconductor compounds SnSe and SnS

Abstract

We conduct comprehensive investigations of both thermal and electrical transport properties of SnSe and SnS using first-principles calculations combined with the Boltzmann transport theory. Due to the distinct layered lattice structure, SnSe and SnS exhibit similarly anisotropic thermal and electrical behaviors. The cross-plane lattice thermal conductivity $\kappa_{L}$ is 40-60% lower than the in-plane values. Extremely low $\kappa_{L}$ is found for both materials because of high anharmonicity. It is suggested that nanostructuring would be difficult to further decrease $\kappa_{L}$ because of the short mean free paths of dominant phonon modes (1-30 nm at 300 K) while alloying would be efficient in reducing $\kappa_{L}$ considering that the relative $\kappa_{L}$ contribution ($\sim$ 65%) of optical phonons is remarkably large. On the electrical side, the anisotropic electrical conductivities are mainly due to the different effective masses of holes and electrons along the $a$, $b$ and $c$ axes. This leads to the highest optimal $ZT$ values along the $b$ axis and lowest ones along the $a$ axis in both $p$-type materials. However, the $n$-type ones exhibit the highest $ZT$s along the $a$ axis due to the enhancement of power factor when the chemical potential gradually approaches the secondary band valley that causes significant increase in electron mobility and density of states. SnSe exhibits larger optimal $ZT$s compared with SnS in both $p$-type and $n$-type materials. For both materials, the peak $ZT$s of $n$-type materials are much higher than those of $p$-type ones along the same direction. The predicted highest $ZT$ values at 750 K are 1.0 in SnSe and 0.6 in SnS along the $b$ axis for the $p$-type doping while those for the $n$-type doping reach 2.7 in SnSe and 1.5 in SnS along the $a$ axis, rendering them among the best bulk thermoelectric materials for large-scale applications.