Compositional Effects and Electron Lone-pair Distortions in Doped Bournonites

Abstract

Bornite materials are naturally occurring systems composed of earth-abundant constituents. Bournonite, a representative of this class of materials, is of interest for thermoelectric applications due to its inherently low thermal conductivity, which has been attributed to the lattice distortions due to stereochemically active electron lone pair distributions. In this computational and experimental study, we present analyses of the lattice structure, electron and phonon dynamics, and charge localization and transfer properties for undoped and Ni and Zn doped bournonites. The results from our simulations reveal complex relations between bond length and bond angle characteristics, chemical bonding, and charge transfer upon doping. Analysis of the experimental results indicate that a microscopic description for bournonite and its doped compositions is necessary for a complete understanding of these materials, as well as for effective control of the transport properties for targeted applications.

Keywords: bournonites; density functional theory; first-principles simulations; thermal conductivity; thermoelectricity.