Lone-Pair-Like Interaction and Bonding Inhomogeneity Induce Ultralow Lattice Thermal Conductivity in Filled β-Manganese-Type Phases.

Finding a way to interlink heat transport with the crystal structure and order/disorder phenomena is crucial for designing materials with ultralow lattice thermal conductivity. Here, we revisit the crystal structure and explore the thermoelectric properties of several compounds from the family of the filled β-Mn-type phases GaTe ( = Pb, Sn, Ca, Na, Na + Ag). The strongly disturbed thermal transport observed in the investigated materials originates from a three-dimensional Te-Ga network with lone-pair-like interactions, which results in large variations of the Ga-Te and -Te interatomic distances and substantial anharmonic effects. In the particular case of NaAgGaTe, the additional presence of different cations leads to bonding inhomogeneity and strong structural disorder, resulting in a dramatically low lattice thermal conductivity (∼0.25 Wm K at 298 K), being the lowest among the reported β-Mn-type phases. This study offers a way to develop materials with ultralow lattice thermal conductivity by considering bonding inhomogeneity and lone-pair-like interactions.