First-principles calculation of P-type Mg3Sb2 thermoelectric performance modification by Ge and Si doping

Mg3Sb2 has been considered a highly promising thermoelectric material for mid-temperature applications. Optimizing the properties of the material is crucial for accelerating its commercial use. In this work, first-principles molecular simulations of P-type Mg3Sb2 doped with the carbon group elements Ge and Si have been carried out. Results indicate that doping with Ge and Si enhances the thermodynamic stability and electrical conductivity of the material. This improvement is achieved by decreasing the bandgap, increasing the local and peak density of states, flattening the band structure, and elevating the relative mass of carriers. Additionally, doping with Ge and Si decreases the phonon velocity and Debye temperature, which weakens the thermal transport properties of the material. These findings suggest that Ge and Si doping is an effective method for improving the thermoelectric properties of the material. At the same doping concentration, the Si single-doped system possesses the smallest bandgap value with the highest peak density of states and forms an indirect bandgap, leading to the best electrical transport properties; the Ge single-doped system has the lowest phonon velocity and Debye temperature, which has the most significant effect in attenuating the thermal transport properties of the material; and the Ge–Si co-doped system has the highest relative mass of carriers, which is conducive to the enhancement of Seebeck coefficient. The results offer theoretical guidance for experimentally analyzing the effects of Ge and Si doping on the thermoelectric properties of Mg3Sb2.