Charge Disproportionation Triggers Bipolar Doping in FeSb_{2- x}Sn _xSe₄ Ferromagnetic Semiconductors, Enabling a...

Ferromagnetic semiconductors (FMSs) featuring a high Curie transition temperature ( T_c) and a strong correlation between itinerant carriers and localized magnetic moments are of tremendous importance for the development of practical spintronic devices. The realization of such materials hinges on the ability to generate and manipulate a high density of itinerant spin-polarized carriers and the understanding of their responses to external stimuli. In this study, we demonstrate the ability to tune magnetic ordering in the p-type FMS FeSb_{2- x}Sn _xSe₄ (0 ≤ x ≤ 0.20) through carrier density engineering. We found that the substitution of Sb by Sn FeSb_{2- x}Sn _xSe₄ increases the ordering of metal atoms within the selenium crystal lattice, leading to a large separation between magnetic centers. This results in a decrease in the T_c from 450 K for samples with x ≤ 0.05 to 325 K for samples with 0.05 < x ≤ 0.2. In addition, charge disproportionation arising from the substitution of Sb³⁺ by Sn²⁺ triggers the partial oxidation of Sb³⁺ to Sb⁵⁺, which is accompanied by the generation of both electrons and holes. This leads to a drastic decrease in the electrical resistivity and thermopower simultaneously with a large increase in the magnetic susceptibility and saturation magnetization upon increasing Sn content. The observed bipolar doping induces a very interesting temperature-induced quantum electronic transition (Lifshitz transition), which is manifested by the presence of an anomalous peak in the resistivity curve simultaneously with a reversal of the sign of a majority of the charge carriers from hole-like to electron-like at the temperature of maximum resistivity. This study suggests that while there is a strong correlation between the overall magnetic moment and free carrier spin in FeSb_{2- x}Sn _xSe₄ FMSs, the magnitude of the Curie temperature strongly depends on the spatial separation between localized magnetic centers rather than the concentration of magnetic atoms or the density of itinerant carriers.