Cationic disorder: Governing the spin-insulatronic properties of nanocrystalline ZnFe$_2$O$_4$ thin films
Résumé
Controlling cation order/disorder in spinel offers a highly effective means of tailoring material properties by modifying inter- and intra-sub-lattice ionic interactions. In this study, we conducted high-temperature magnetization measurements (300–1000 K) to determine average Curie temperatures (TC) for nanocrystalline ZnFe$_2$O$_4$ thin films. Thermodynamical stability of these films under extreme conditions was investigated by assessing lattice structures, oxygen vacancies, magnetization, and electric resistivity for spin-insulatronic applications. Reversible cation inversion via heat treatments (in-situ and ex-situ) yields tunable ferrimagnetic (FiM) order in ZnFe$_2$O$_4$, with TC ranging from 425 to 710 K. First-principles calculations highlight effective cation inversion mitigating magnetic frustration, promoting collinear FiM ordering, and elevating TC. Oxygen vacancies further reinforce ferrimagnetism, slightly reducing resistivity through the formation of Fe-3d gap states near the Fermi level. A proposed magnetic nanophase diagram elucidates dominant competing magnetic ground states (cluster spin-glassy state, FiM, and antiferromagnetic) with increasing growth temperature, fostering innovative homo-architectures from multiple ZnFe$_2$O$_4$ thin films with diverse functionalities.
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