Electronic structure of K2Bi8Se13 -: art. no. 085116

K2Bi8Se13 belongs to a class of complex chalcogenides that shows potential for superior thermoelectric performance. This compound forms in two distinct phases, alpha and beta. The beta phase, which has several sites with mixed K/Bi occupancy, is a better thermoelectric. To understand the origin of this difference between the two phases we have carried out electronic structure calculations within ab initio density functional theory using the full potential linearized augmented plane wave (FLAPW) method. Both the local spin density approximation (LSDA) and the generalized gradient approximation (GGA) were used to treat the exchange and correlation potential. The spin-orbit interaction (SOI) was incorporated using a second variational procedure. The a phase is found to be a semiconductor with an indirect LSDA/GGA band gap of 0.38 eV/0.46 eV compared to 0.76 eV for the observed direct optical gap. For the beta phase we have chosen two different ordered structures with extreme occupancies of K and Bi atoms at the "mixed sites." The system is found to be a semimetal for both the ordered structures. To incorporate the effect of mixed occupancy we have chosen a 1 X 1 X 2 supercell with an alternative K/Bi occupancy at the mixed sites. The system is a semiconductor with an indirect LSDA/GGA band gap of 0.32 eV/0.41 eV. We find that the mixed occupancy is crucial for the system to be a semiconductor because the Bi atoms at the mixed sites stabilize the p orbitals of the nearest-neighbor Se atoms by lowering their energy. We also find a strong anisotropy in the effective mass near the conduction band minimum, with the smallest effective mass along the mixed K/Bi chains (parallel to the c axis). This large anisotropy suggests that beta-K2Bi8Se13 has a great potential for an n-type thermoelectric.