Half-Heusler-like compounds with wide continuous compositions and tunable p- to n-type semiconducting thermoelectrics

Half-Heusler and full-Heusler compounds were considered as independent phases with a natural composition gap. Here we report the discovery of TiRu1+xSb (x = 0.15 ~ 1.0) solid solution with wide homogeneity range and tunable p- to n-type semiconducting thermoelectrics, which bridges the composition gap between half- and full-Heusler phases. At the high-Ru end, strange glass-like thermal transport behavior with unusually low lattice thermal conductivity (~1.65 Wm−1K−1 at 340 K) is observed for TiRu1.8Sb, being the lowest among reported half-Heusler phases. In the composition range of 0.15 < x < 0.50, TiRu1+xSb shows abnormal semiconducting behaviors because tunning Ru composition results in band structure change and carrier-type variation simultaneously, which seemingly correlates with the localized d electrons. This work reveals the possibility of designing fascinating half-Heusler-like materials by manipulating the tetrahedral site occupancy, and also demonstrates the potential of tuning crystal and electronic structures simultaneously to realize intriguing physical properties.