Temperature Induced Band Convergence, Intervalley Scattering, and Thermoelectric Transport in p-Type PbTe

Achieving high valley degeneracy (i.e., "band convergence") in a material usually results in considerably enhanced thermoelectric properties. However, it is still unclear why this strategy of designing efficient thermoelectric materials is so successful, because the benefit of increased density of states may be severely degraded by intervalley scattering. Using first-principles calculations, we investigate these effects in p-type PbTe, where temperature induces alignment of the L and Sigma valleys at similar to 620 K. We explicitly show that the thermoelectric power factor and figure of merit peak near the band convergence temperature. The figure of merit maximum is larger than those of the individual L and Sigma valleys. Surprisingly, intervalley scattering does not considerably affect the figure of merit near the band convergence temperature and optimal doping conditions, although it reduces the power factor by almost a factor of 2. Our results suggest that band convergence will significantly increase the figure of merit if intervalley scattering is roughly proportional to the density of states and the lattice thermal conductivity is considerably lower than the electronic thermal conductivity, even if intervalley scattering is strong.