High Thermoelectric Performance Lead Selenide Materials through All-scale Hierarchical Structuring

Industries have paid increasing attention to power generation using waste heat through thermoelectrics, which convert heat to electric energy. This method can be used in renewable applications because of its environmentally friendly process. Large-scale production of bulk materials with high thermoelectric figure of merit (ZT) is the key to practical applications. PbTe-based materials have been mostly studied, but are facing a challenge regarding scarcity of Te. PbSe is a more abundant analog of PbTe that has been less frequently studied. This work presents a synthesis and characterization of bulk thermoelectric materials based on both n- and p-type PbSe with atomic-, nano-, meso-scale architectures.;When PbSe is doped with Ga and In they efficiently generate electron carriers that are sufficient for high ZT. Thus, higher ZT of n-type PbSe can be achieved than that of optimized n-type PbTe at high temperatures. The study of the thermoelectric properties of p-type PbSe with Li, Na, and K indicates that the efficiency of Na in doping PbSe is found to be the highest. The additional spark plasma sintering (SPS) process allows samples to have increased carrier density and produce mesoscale grains that reduce lattice thermal conductivity, increasing ZT.;Additional studies for reducing lattice thermal conductivity through nanostructuring were conducted. Adding (Ca/Sr/Ba)Se and EuSe to Na doped SPS PbSe generates nanoprecipitates. This study shows that the hierarchical architecture on the atomic scale (Na and Ca/Sr/Ba/Eu solid solution), nanoscale (MSe/EuSe nanoprecipitates), and mesoscale (grains) effectively increases ZT. MSe samples show no appreciable change in charge transport, while EuSe samples show decreased charge carriers. However, adding more Na optimizes properties.;Continued investigating n-type dopants with Sb and Bi shows that Sb not only plays the role as a dopant but also is unexpectedly effective in generating nanostructuring. The Sb-rich precipitates appear remarkably effective in reducing the lattice thermal conductivity. The corresponding Bi samples exhibit few precipitates and smaller reduction in lattice thermal conductivity. An exceptional performance for Sb-doped PbSe can be obtained and this in sharp contrast to Bi-doped PbSe.