Exploiting Mismatch Strain and the β–α Phase Transition for Microstructural Engineering in Thermoelectric Ag2Se

Silver selenide (Ag2Se) is a promising near-room-temperature thermoelectric material, but its narrow stoichiometric window and β–α phase transition complicate reproducible microstructure control. Here, we present a mismatch-assisted microstructure engineering strategy in which Ag2Se particles are treated with polyanionic ZnSe complexes and consolidated through the β–α transition to introduce ZnSe nanoprecipitates, Ag2Se/ZnSe interfaces, and local strain fields. The crystallographic mismatch between ZnSe and Ag2Se, together with the Zn2+/Ag+ size difference, amplifies phase-transition-induced deformation and promotes high-density dislocations with periodic strain modulations. This defect architecture suppresses grain coarsening, removes excess Ag, limits Ag-interstitial formation, and reduces lattice thermal conductivity through lattice softening and multiscale phonon scattering. Ag2Se–4%ZnSe nanocomposites achieve a peak zTmax of 1.13 at 369 K and a zTavg of 1.08 from 300 to 380 K, demonstrating mismatch-driven defect engineering through the β–α phase transition as a route for optimizing Ag2Se-based thermoelectrics.