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The power factor of pure p-type ZnSb has been calculated via ab initiosimulations assuming that the carrier concentrations are due to the dopingeffect of intrinsic zinc vacancies. With a vacancy concentration close to theexperimental solubility limit we were able to perfectly reproduce the PowerFactor measured in polycrystalline ZnSb samples. The methodology has then beensuccessfully extended for predicting the effect of extrinsic doping elements onthe thermoelectric properties of ZnSb. Germanium and tin seem to be promisingp-type doping elements. In addition, we give, for the first time, anexplanation of why it is difficult to synthesize polycrystalline n-type ZnSbsamples. Indeed, compensative effects between intrinsic defects (zincvacancies) and doping elements (Ga, or In) explain the existence of an optimal(and relatively high) dopant concentration necessary to convert ZnSb into ann-type semiconductor.

Thermoelectric power factor of pure and doped ZnSb via DFT based defect calculations