Anisotropic Phonon Heat Flow and Thermoelectric Response in Tetragonal GeS$_2$ and GeSe$_2$

Abstract

The electronic structure, lattice dynamics, bonding, elastic response, and anisotropic thermoelectric transport properties of tetragonal GeS$_2$ and GeSe$_2$ were investigated using density functional theory, density functional perturbation theory, Wannier interpolation, and scattering-aware Boltzmann transport. The relaxed structures are mechanically and dynamically stable within the calculated harmonic description. The HSE03/Wannier band gaps are 2.48 eV for GeS$_2$ and 1.23 eV for GeSe$_2$, while substitution of S by Se lowers the upper phonon frequency from approximately 13.6 to 10.3 THz. The phonon Boltzmann transport calculations reveal pronounced lattice-transport anisotropy. Within the relaxation-time approximation, the 300 K in-plane and cross-plane lattice thermal conductivities are 26.86 and 1.19 W m$^{-1}$ K$^{-1}$ for GeS$_2$, and 18.74 and 1.52 W m$^{-1}$ K$^{-1}$ for GeSe$_2$, respectively. At 800 K, these values decrease to 10.22 and 0.46 W m$^{-1}$ K$^{-1}$ for GeS$_2$, and 7.25 and 0.58 W m$^{-1}$ K$^{-1}$ for GeSe$_2$. Frequency-resolved analysis shows that low-frequency phonons carry most of the heat, whereas the small cross-plane values reflect restricted out-of-plane phonon transport. Combining the ShengBTE RTA lattice tensors with AMSET electronic coefficients gives $zT=0.257$ for n-type cross-plane GeS$_2$ at 800 K and $10^{19}$ cm$^{-3}$. The corresponding PBE-AMSET estimate for GeSe$_2$ is $zT=0.066$ for p-type cross-plane transport at 800 K and $3\times10^{20}$ cm$^{-3}$. LOBSTER analysis identifies mixed covalent--ionic Ge--X bonding, with Ge--S bonds having a larger stabilizing ICOHP magnitude than Ge--Se bonds ($-5.27$ versus $-4.74$ eV per bond). These results identify tetragonal GeX$_2$ compounds as strongly anisotropic thermoelectrics with moderate calculated $zT$ values whose cross-plane response benefits from suppressed lattice heat transport.