Chemical Pressure-Driven Band Convergence and Discordant Atoms Intensify Phonon Scattering Leading to High Thermoelectric Performance in SnTe

SnTe is an intriguing alternative to PbTe for midtemperature thermoelectric applications. Despite steady progress, its performance is lagging, in part because of the large energy difference(Δ<i>E</i>_L-Σ) between the light (L-band) and heavy (Σ-band) valence bands and higher lattice thermal conductivity (κ_L). Previous studies have shown that applying pressure can enhance the Seebeck coefficient (<i>S</i>) and power factor (<i>PF</i>) of SnTe. Inspired by this study, we showcase how the high-pressure effect can be emulated under ambient pressure by substituting Sn with atoms possessing smaller atomic radii. Specifically, Sb- and Ge-doping combined with CdTe- or CdS-alloying induce lattice shrinkage, also referred to as "chemical pressure", raising the energy of the Σ-band. Additionally, these substituted atoms lower the contribution of Sn 5s-Te 5p antibonding states to the L-band, thereby reducing its energy and dispersion. These combined effects decrease Δ<i>E</i>_L-Σ from 0.36 to 0.09 eV, leading to the enhanced <i>S</i> and average <i>PF</i>_avg. Notably, the <i>PF</i>_avg, ranging from 323 to 873 K, increases from 8.1 μW cm^-1 K^-2 for pristine SnTe to 21.6 μW cm^-1 K^-2 for Sn_0.79Ge_0.15Sb_0.06Te-5% CdTe. Furthermore, the intensified phonon scattering resulting from discordant nature of Ge and Cd atoms, creating point defects soften phonon modes, and the presence of Ge-rich nanoprecipitates lead to a substantial 62% reduction in κ_L at 873 K. This strong valence band convergence and enhanced phonon scattering collectively contribute to a high peak <i>ZT</i> of 1.5 (873 K) and high average <i>ZT</i>_avg = 0.81 over the temperature range of 323-873 K.