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The thermoelectric properties of PbSe have significantly improved in recentyears reaching figures of merit ZT 1.6. The transport properties of the holedoped high temperature thermoelectric material PbSe are particularlyinteresting and play a key role in this. Here they were analyzed over a widetemperature and hole concentration ranges. The special features observed in thevariation of the experimental Seebeck coefficient, and Hall coefficient can beaccounted for within the framework of a two band model. Two valence bandsseparated by a temperature dependent energy offset are considered. The extremumof the light hole band has a density of states mass 0.27mo at room temperature.It is non-parabolic and anisotropic and can be described by the Kane model. Theextremum of the heavy hole band is isotropic and parabolic with a much largerdensity of states mass 2.5mo. We find that for heavily doped compositions thehigh mass band contributes the Seebeck coefficient even at room temperature.With rising temperature holes are transferred from the light hole to the heavyhole branch giving rise to the anomalous temperature dependent Hall coefficientwhich is found peaked near 650 K.

Understanding the role and interplay of heavy hole and light hole valence bands in the thermoelectric properties of PbSe