Vacancy-Driven Noncubic Local Structure and Magnetic Anisotropy Tailoring in FexO−Fe3−δO4 Nanocrystals

In contrast to bulk materials, nanoscale crystal growth is critically influenced by size- and shape-dependent properties. However, it is challenging to decipher how stoichiometry, in the realm of mixed-valence elements, can act to control physical properties, especially when complex bonding is implicated by short- and long-range ordering of structural defects. Here, solution-grown iron-oxide nanocrystals (NCs) of the pilot wüstite system are found to convert into iron-deficient rock-salt and ferro-spinel subdomains but attain a surprising tetragonally distorted local structure. Cationic vacancies within chemically uniform NCs are portrayed as the parameter to tweak the underlying properties. These lattice imperfections are shown to produce local exchange-anisotropy fields that reinforce the nanoparticles’ magnetization and overcome the influence of finite-size effects. The concept of atomic-scale defect control in subcritical-size NCs aspires to become a pathway to tailor-made properties with improved performance for hyperthermia heating over defect-free NCs.