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Thermoelectric materials operating at cryogenic temperatures are in highdemand for efficient cooling and power generation in applications ranging fromsuperconductors to quantum computing. The narrow band-gap semiconductor FeSb2,known for its colossal Seebeck coefficient, holds promise for suchapplications, provided its thermal conductivity value can be reduced. Thisstudy investigates the impact of isoelectronic substitution (Bi) and holedoping (Pb) at the Sb site on the transport properties of FeSb2, with aparticular focus on thermal conductivity (\k{appa}). Polycrystalline FeSb2powder, along with Bi- and Pb-doped samples, were synthesized using a simpleco-precipitation approach, followed by thermal treatment in an H2 atmosphere.XRD and SEM analysis confirms the formation of the desired phase pre- andpost-consolidation using spark plasma sintering (SPS). The consolidationprocess resulted in a high compaction density and the formation ofsubmicrometer-sized grains, as substantiated by electron backscattereddiffraction (EBSD) analysis. Substituting 1% of Bi and Pb at the Sb sitesuccessfully suppressed the thermal conductivity (\k{appa}) from ~15 W/m-K inpure FeSb2 to ~10 and ~8.7 W/m-K, respectively. Importantly, resistivitymeasurements revealed a metal-to-insulator transition at around 6.5 K inundoped FeSb2 and isoelectronically Bi-substituted FeSb2, suggesting theexistence of metallic surface states and provides valuable evidence for theperplexing topological behavior exhibited by FeSb2.

Transport and electrical properties of cryogenic thermoelectric FeSb2: the effect of isoelectronic and hole doping