Synergistic Sn-Induced Band Convergence in Mn-Doped p-Type PbTe Enables High Thermoelectric Performance

The inherent coupling of electrical and thermal transport parameters poses a significant challenge for enhancing the thermoelectric figure of merit (zT) in PbTe-based materials. Herein, we report a synergistic co-doping strategy employing Mn and Sn in p-type PbTe to simultaneously optimize the band structure and suppress lattice thermal conductivity. Sn incorporation not only induces additional Pb vacancies, thereby increasing hole carrier concentration, but also facilitates the enhanced solubility of Na dopants within the matrix, as confirmed by microscopic and compositional analyses. More importantly, the cooperative effect of Mn and Sn substantially enhances convergence between the L and Σ valence bands, leading to an increased density-of-states effective mass and a pronounced enhancement of the Seebeck coefficient. Meanwhile, multiscale lattice defects introduced by co-doping effectively scatter phonons over a broad frequency spectrum, reducing the lattice thermal conductivity to near the theoretical minimum (~0.5 W m−1 K−1). As a result, the Pb0.91−xNa0.04Mn0.04SnxTe system achieves an exceptional peak zT of ~2.2 at 823 K, a high room-temperature zT of ~0.4, and a favorable average zT of ~1.3 over the temperature range of 303–823 K. Notably, the room-temperature zT of ~0.4 represents the highest value reported to date for p-type PbTe in the room-temperature region. This work demonstrates that Mn and Sn co-doping provides a compelling pathway for realizing both high peak and average thermoelectric performance, advancing PbTe-based materials toward practical waste-heat recovery applications.