Multiple Roles of Unconventional Heteroatom Dopants in Chalcogenide Thermoelectrics: The Influence of Nb on Transport and Defects in BiTe.

Improvements in the thermoelectric performance of n-type BiTe materials to more closely match their p-type counterparts are critical to promote the continued development of bismuth telluride thermoelectric devices. Here the unconventional heteroatom dopant, niobium, has been employed as a donor in BiTe. Nb substitutes for Bi in the rhombohedral BiTe structure and exhibits multiple roles in its modulation of electrical transport and defect-induced phonon scattering. The carrier concentration is significantly increased as electrons are afforded by aliovalent doping and formation of vacancies on the Te sites. In addition, incorporation of Nb in the pseudoternary BiNbTe system increases the effective mass, , which is consistent with cases of "conventional" elemental doping in BiTe. Lastly, inclusion of Nb induces both point and extended defects (tellurium vacancies and dislocations, respectively), enhancing phonon scattering and reducing the thermal conductivity. As a result, an optimum of 0.94 was achieved in n-type BiNbTe at 505 K, which is dramatically higher than an equivalent undoped BiTe sample. This study suggests not only that is Nb an exciting and novel electron dopant for the BiTe system but also that unconventional dopants might be utilized with similar effects in other chalcogenide thermoelectrics.