Effects of Preparation Procedures and Porosity on Thermoelectric Bulk Samples of Cu₂SnS₃ (CTS)

The thermoelectric behavior and stability of Cu₂SnS₃ (CTS) has been investigated in relation to different preparations and sintering conditions, leading to different microstructures and porosities. The studied system is CTS in its cubic polymorph, produced in powder form via a bottom-up approach based on high-energy reactive milling. The as-milled powder was sintered in two batches with different synthesis conditions to produce bulk CTS samples: manual cold pressing followed by traditional sintering (TS), or open die pressing (ODP). Despite the significant differences in densities, ~75% and ~90% of the theoretical density for TS and ODP, respectively, we observed no significant difference in electrical transport. The stable, best performing TS samples reached zT ~0.45, above 700 K, whereas zT reached ~0.34 for the best performing ODP in the same conditions. The higher zT of the TS sintered sample is due to the ultra-low thermal conductivity (κ ~0.3-0.2 W/mK), three-fold lower than ODP in the entire measured temperature range. The effect of porosity and production conditions on the transport properties is highlighted, which could pave the way to produce high-performing TE materials.