Lead Vacancy Promotes Sodium Solubility to Achieve Ultra‐High zT in Only Ternary Pb_1‐xNa_xTe

Abstract Chemical doping of sodium is an indispensable means to optimize thermoelectric properties of PbTe materials, while a bottleneck is that an aliovalent atom doping leads to spontaneous intrinsic defects in the PbTe matrix, resulting in low dopant solubility. Therefore, it is urgent to improve the doping efficiency of Na for maximizing optimization. Here, an amazing new insight that the intentionally introduced Pb vacancies can promote Na solubility in ternary Pb_1‐xNa_xTe is reported. Experimental analysis and theoretical calculations provide new insights into the inherent mechanism of the enhancement of Na solubility. The Pb vacancies and the resultant more dissolved Na not only synergistically optimize the carrier concentration and further facilitate the band convergence, but also induce a large number of dense dislocations in the grains. Consequently, benefiting from the self‐enhancement of Seebeck coefficient and the minimization of lattice thermal conductivity, an 18% growth is obtained for the figure of merit zT in vacancy‐containing Pb_0.95Na_0.04Te sample, reaching maximum zT_max ≈ 2.0 at 823 K, which achieves an ultra‐high performance in only Na‐doped ternary Pb_1‐xNa_xTe materials. The strategy utilized here provides a novel route to optimize PbTe materials and represents an important step forward in manipulating thermoelectrics to improve dopant solubility.