Mn alloying in thermoelectrics is a long-standing strategy for enhancing their figure-of-merit through optimizing electronic transport properties by band convergence, valley perturbation, or spin-orbital coupling. By contrast, mechanisms by which Mn contributes to suppressing thermal transports, namely thermal conductivity, is still ambiguous. A few precedent studies indicate that Mn introduces a series of hierarchical defects from the nano- to meso-scale, leading to effective phonon scattering scoping a wide frequency spectrum. Due to insufficient insights at the atomic level, the theory remains as phenomenological and cannot be used to quantitatively predict the thermal conductivity of Mn-alloyed thermoelectrics. Herein, by choosing the SnTe as a case study, aberration-corrected transmission electron microscopy (TEM)/scanning transmission electron microscopy (STEM) to characterize the lattice complexity of Sn1.02- x Mnx Te is employed. Mn as a "dynamic" dopant that plays an important role in SnTe with respect to different alloying levels or post treatments is revealed. The results indicate that Mn precipitates at x = 0.08 prior to reaching solubility (≈10 mol%), and then splits into MnSn substitution and γ-MnTe hetero-phases via mechanical alloying. Understanding such unique crystallography evolution, combined with a modified Debye-Callaway model, is critical in explaining the decreased thermal conductivity of Sn1.02- x Mnx Te with rational phonon scattering pathways, which should be applicable for other thermoelectric systems.
Keywords: Mn alloying; SnTe; electron microscopy; structural evolution; thermoelectric materials.
© 2021 Wiley-VCH GmbH.