Zhong-Zhen Luo | Searcharxiv

arXiv2025

Low and Anisotropic Thermal Conductivity in Mixed-Valent Sn$_2$S$_3$

Compounds of Sn, such as SnSe and SnS, exhibit novel phonon characteristics and low thermal conductivity, making them emerging star materials in the thermoelectric family. In this work, through the Boltzmann transport equation scheme and the Wigner thermal transport model, quasi-1D mixed-valent Sn$_2$S$_3$ were found to exhibit a low thermal conductivity along c-axis with a weak temperature dependence. The low thermal conductivity is attributed to the anharmonic rattling vibrations of weakly bonded Sn(II) atoms, which are influenced by the coulomb interaction of lone pairs at adjacent Sn(II) atoms. The rattling of Sn(II) induces low-frequency flat optical phonons and avoids crossing behavior. The atomic displacements and mean square displacement (MSD) analysis reveal that Sn(II) atoms exhibit significantly greater and anisotropic displacements compared to Sn(IV) and S, confirming that Sn(II) behaves as a rattler. The results obtained from this work suggest an opportunity to discover low thermal conductivity in mixed-valent compounds.

cond-mat.mtrl-sci↗

arXiv2023

Dynamic crystallography reveals spontaneous anisotropy in cubic GeTe

Cubic energy materials such as thermoelectrics or hybrid perovskite materials are often understood to be highly disordered. In GeTe and related IV-VI compounds, this is thought to provide the low thermal conductivities needed for thermoelectric applications. Since conventional crystallography cannot distinguish between static disorder and atomic motions, we develop the energy-resolved variable-shutter pair distribution function technique. This collects structural snapshots with varying exposure times, on timescales relevant for atomic motions. In disagreement with previous interpretations, we find the time-averaged structure of GeTe to be crystalline at all temperatures, but with anisotropic anharmonic dynamics at higher temperatures that resemble static disorder at fast shutter speeds, with correlated ferroelectric fluctuations along the $<$100$>$c direction. We show that this anisotropy naturally emerges from a Ginzburg-Landau model that couples polarization fluctuations through long-range elastic interactions. By accessing time-dependent atomic correlations in energy materials, we resolve the long-standing disagreement between local and average structure probes, and show that spontaneous anisotropy is ubiquitous in cubic IV-VI materials.

cond-mat.mtrl-sci↗