Glass-like anomalies and unconventional thermoelectric transport in chimney ladder crystals

Abstract

Nowotny chimney ladder (NCL) crystals present physical properties in between the contrasting paradigms of ideal crystal and amorphous solid, making them promising candidates for thermoelectric applications due to their inherently low thermal conductivity. In this work, we report an extensive experimental characterization of the thermodynamic and thermoelectric transport properties of a large class of NCL materials, focusing on the intermetallic compound Ru$_2$Sn$_{3}$. We show that, despite their ordered crystalline structure, the heat capacity of these NCL compounds deviates from the Debye model at low temperatures and exhibits a boson-peak-like glassy anomaly in the range of $8$-$14$ K. By combining experimental measurements with density functional theory (DFT) and \emph{ab initio} molecular dynamics (AIMD) simulations, we attribute the microscopic origin of this glassy behavior to extremely low-energy optical phonons that universally emerge from the chimney ladder sublattice structure. Crucially, their coupling to acoustic phonons induces hybridization and avoided crossings, leading to strongly modified acoustic modes that directly contribute to the anomaly as well, similar to the case of other thermoelectric materials such as clathrates. Additionally, the measured thermal conductivity and the thermoelectric response present distinct anomalous glass-like features that strongly correlate with the dynamics of the low-lying optical phonons revealed by simulations. In particular, the electric resistivity displays an extended linear in $T$ behavior and an anomalously large $T^2$ contribution at low temperature. We propose a simple theoretical framework, based on electrons scattering with overdamped phononic modes, that qualitative explains both these features.