High Thermoelectric Performance in PbSe–NaSbSe2 Alloys from Valence Band Convergence and Low Thermal Conductivity

PbSe is an attractive thermoelectric material due to its favorable electronic structure, high melting point, and lower cost compared to PbTe. Herein, the hitherto unexplored alloys of PbSe with NaSbSe₂ (NaPb_mSbSe_m+2) are described and the most promising p‐type PbSe‐based thermoelectrics are found among them. Surprisingly, it is observed that below 500 K, NaPb_mSbSe_m+2 exhibits unorthodox semiconducting‐like electrical conductivity, despite possessing degenerate carrier densities of ≈10²⁰ cm^?3. It is shown that the peculiar behavior derives from carrier scattering by the grain boundaries. It is further demonstrated that the high solubility of NaSbSe₂ in PbSe augments both the thermoelectric properties while maintaining a rock salt structure. Namely, density functional theory calculations and photoemission spectroscopy demonstrate that introduction of NaSbSe₂ lowers the energy separation between the L‐ and Σ‐valence bands and enhances the power factors under 700 K. The crystallographic disorder of Na⁺, Pb²⁺, and Sb³⁺ moreover provides exceptionally strong point defect phonon scattering yielding low lattice thermal conductivities of 1–0.55 W m^‐1 K^‐1 between 400 and 873 K without nanostructures. As a consequence, NaPb₁₀SbSe₁₂ achieves maximum ZT ≈1.4 near 900 K when optimally doped. More importantly, NaPb₁₀SbSe₁₂ maintains high ZT across a broad temperature range, giving an estimated record ZT_avg of ≈0.64 between 400 and 873 K, a significant improvement over existing p‐type PbSe thermoelectrics.