Oxygen vacancy-induced short-range ordering as a sole mechanism for enhanced magnetism of spinel ZnFe2O4 prepared via a one-step treatment

Abstract

Despite being difficult to identify, extremely dilute oxygen vacancies have been widely reported to play an important role in enhancing magnetism in ZnFe2O4. The mechanisms underlying this enhanced magnetism have not been well understood for a long time and remain controversial because the formation of oxygen vacancy-rich ZnFe2O4 can be accompanied by changes in the chemical/physical characteristics, especially the composition, particle size, surface morphology and cation distribution, which can significantly affect the magnetization. An open and important question is whether and to what extent the enhanced magnetization can be attributed only to oxygen vacancies. In this study, the relationship between the magnetization and oxygen vacancies in ZnFe2O4 was definitively determined by using a carefully designed “shake-and-heat” treatment to prepare vacancy-rich samples while keeping the other crystal/surface parameters constant. Compared to the nearly vacancy-free paramagnetism samples, the vacancy-rich samples exhibited a higher magnetization of approximately 5 emu/g at both 300 K and 2 K. The Fe3+-O2--Fe3+ superexchange paths broken by oxygen vacancies then resulting in the Fe3+-Fe3+ ferromagnetism configuration. Meanwhile, the oxygen vacancy is highly diluted then the ferromagnetism configuration is confined in a single super-cell, favoring a short-range magnetic ordering at room temperature. The concentration of oxygen vacancies was calculated to be 0.68% by magnetization measurement. Our results may shed a light on how oxygen vacancies affect magnetism.