Low-Dimensional Structure Modulation in Ag8SnSe6 for Enhanced Thermoelectric Performance

Ternary liquid-like thermoelectric materials have garnered significant attention due to their ultra-low lattice thermal conductivity. Among these, Ag₈SnSe₆ stands out for its exceptionally low sound velocity and thermal conductivity. However, the inherent poor electrical conductivity and suboptimal thermoelectric properties of Ag₈SnSe₆ necessitate further improvement. Here, a novel approach is initiated to enhance the thermoelectric properties of Ag₈SnSe₆ by combining low-dimensionalization with intrinsic doping. For the first time, this work successfully synthesizes single-phase Ag₈SnSe₆ nanocrystals, ≈10 nm in size, with the correct phase and composition using a robust and reliable colloidal method. This approach represents a significant improvement over previous reports on this material. Reducing the crystal domains of Ag₈SnSe₆ to the nanoscale induces quantum confinement effects, increasing the density of states near the Fermi surface. It also introduces additional grain boundaries, which lower the lattice thermal conductivity and simplify structural design. Moreover, incorporating small amounts of Sn nanopowder into the Ag₈SnSe₆ nanocrystals before consolidation further enhances the thermoelectric performance. Sn acts as a donor dopant, increasing the electronic concentration while at the same time improving their mobility by reducing interface barriers, thus significantly improving the material transport properties. Additionally, the presence of Sn leads to the formation of point defects, dislocations, and secondary phases, which increase phonon scattering and further reduce the thermal conductivity. Through this synergistic optimization, the figure of merit shows a significant increase across a wide temperature range. Overall, a strategy is presented for the controlled preparation of Ag₈SnSe₆ nanocrystals, the decoupling of their electrical and thermal transport, and the practical application of this material to thermoelectric single-leg modules.