Role of Lone-Pair Electrons in Producing Minimum Thermal Conductivity in Nitrogen-Group Chalcogenide Compounds

Fully dense crystalline solids with extremely low lattice thermal conductivity (kappa(L)) are of practical importance for applications including thermoelectric energy conversion and thermal barrier coatings. Here we show that lone-pair electrons can give rise to minimum kappa(L) in chalcogenide compounds that contain a nominally trivalent group VA element. Electrostatic repulsion between the lone-pair electrons and neighboring chalcogen ions creates anharmonicity in the lattice, the strength of which is determined by the morphology of the lone-pair orbital and the coordination number of the group VA atom.