Low Thermal Conductivity in Heteroanionic Materials with Layers of Homoleptic Polyhedra

Although BiAgOSe, an analogue of a well-studied thermoelectric material BiCuOSe, is thermodynamically stable, its synthesis is complicated by the low driving force of formation from the stable binary and ternary intermediates. Here we have developed a "subtraction strategy" to suppress byproducts and produce pure phase BiAgOSe using hydrothermal methods. Electronic structure calculations and optical characterization show that BiAgOSe is an indirect bandgap semiconductor with a bandgap of 0.95 eV. The prepared sample exhibits lower lattice thermal conductivities (0.61 W·m^-1·K^-1 at room temperature and 0.35 W·m^-1·K^-1 at 650 K) than BiCuOSe. Lattice dynamical simulations and variable temperature diffraction measurements demonstrate that the low lattice thermal conductivity arises from both the low sound velocity and high phonon-phonon scattering rates in BiAgOSe. These in turn result primarily from the soft Ag-Se bonds in the edge-sharing AgSe₄ tetrahedra and large sublattice mismatch between the quasi-two-dimensional [Bi₂O₂]²⁺ and [Ag₂Se₂]^2- layers. These results highlight the advantages of manipulating the chemistry of homoleptic polyhedra in heteroanionic compounds for electronic structure and phonon transport control.