Achievinga High <i>zT</i>_avg in n‑Type Sb-DopedMg₂Si_0.3Sn_0.7 via High-Pressure-ModulatedMicrostructures

Mg₂Si-based compounds are cost-effective and environmentally friendly thermoelectric materials. However, the current Mg₂(Si,Sn) solid solutions still suffer from the low figure of merit <i>zT</i> (or the low energy conversion efficiency), especially the low averaged <i>zT</i> value (<i>zT</i>_avg < 1.0). In this study, we synthesize the Mg₂(Si_0.3Sn_0.7)_1–<i>x</i>Sb_<i>x</i> (<i>x</i> = 0, 0.5, 0.75, 1, and 1.5%) solid solutions through the combination of high-pressure, high-temperature (HPHT) synthesis and spark plasma sintering (SPS). The high-pressure instrument effectively inhibits the unfavorable oxidation of Mg. This HPHT + SPS methodology improves the defect formation efficiency of Sb-doped Mg₂Si_0.3Sn_0.7, leading to an increased carrier concentration and enhanced electrical conductivity. Moreover, as a benefit from the pressure-induced conduction band convergence and Sb-flattened conduction band, the density of states’ effective mass (<i>m</i>_d*) significantly increases to ∼3.3<i>m</i>_e, maintaining high Seebeck coefficients even at a high carrier concentration. The synergetic effects of doping and <i>m</i>_d* increase the peak power factor to exceed 50 μW cm^–1 K^–2. Notably, due to the HPHT-modified microstructures, the hierarchy phonon scatterings are established to suppress the lattice thermal conductivity to as low as 1.29 W m^–1 K^–1 at 568 K; the Sb point defects, dislocations, and grain boundaries/pores can scatter the short-, medium-, and long-wavelength phonons, respectively. Ultimately, <i>zT</i> of the optimized Mg₂(Si_0.3Sn_0.7)_0.99Sb_0.01 sample increases significantly in the whole temperature region; the <i>zT</i> peak is 1.37 at 673 K, and a high <i>zT</i> plateau of ∼1.35 is realized between 568 and 723 K. Thus, the notable average <i>zT</i> over the range of 323–723 K is 1.08. Our work demonstrates that the high-pressure-induced defect concentration, effective doping, and microstructure modifications facilitate the thermoelectric property improvement in the Mg₂(Si,Sn)-based compounds.