Thermally Controlled Charge‐Carrier Transitions in Disordered PbSbTe Chalcogenides

Abstract Binary and ternary chalcogenides have recently attracted much attention due to their wide range of applications including phase‐change memory materials, topological insulators, photonic switches, and thermoelectrics. These applications require a precise control of the number and mobility of charge carriers. Here, an unexpected charge‐carrier transition in ternary compounds from the PbTe–Sb₂Te₃ pseudo‐binary line is reported. Upon thermal annealing, sputtered thin films of PbSb₂Te₄ and Pb₂Sb₂Te₅ undergo a transition in the temperature coefficient of resistance and in the type of the majority charge carriers from n‐type to p‐type. These transitions are observed upon increasing structural order within one crystallographic phase. To account for this striking observation, it is proposed that the Fermi energy shifts from the tail of the conduction band to the valence band because different levels of overall structural disorder lead to different predominant types of native point defects. This view is confirmed by an extensive computational study, revealing a transition from excess cations and Sb_Pb for high levels of disorder to Pb_Sb prevailing for low disorder. The findings will help fine‐tune transport properties in certain chalcogenides via proper thermal treatment, with potential benefits for memories, thermoelectric material optimization, and neuromorphic devices.