Metastable Crystalline Cobalt Iron Oxide Nano-Flakes with Antiferromagnetic/Ferrimagnetic Composition Mosaicity

By thermal decomposition of a crystalline hydroxycarbonate precursor with a Co:Fe ratio of 2:1, crystals with alternating ferrimagnetic and antiferromagnetic nano-domains were synthesized using a facile synthetic approach that combined bottom-up co-precipitation of the precursor with a self-assembled top-down nano-structuring during spinel formation. Due to the miscibility gap of the spinel phase diagram at this composition, a topotactic segregation into CoFe₂O₄-like and Co₃O₄-like domains takes place at 400 °C, giving rise to porous crystalline nano-flakes with spatial compositional fluctuations on a scale of approximately 5 nm. Experimental methods and density functional theory showed that the metastable nature of this interface-rich material is manifested in the unexpectedly low lattice parameter of the iron-rich domains, which can be explained by the compressive strain executed on this phase due to mosaicity. Investigations of the magnetic properties revealed an exchange bias effect, due to this unique microstructure, which is typically known for thin films or core/shell nanoparticles. Treatment at temperatures higher than 450 °C causes this microstructure to break down, the lattice strain to relax, and finally leads to properties expected for the thermodynamically stable phases according to the phase diagram.