Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals

This paper describes the first synthetic method to achieve independent control over both the cation distribution (quantified by the inversion parameter x) and size of colloidal ZnFe₂O₄ nanocrystals. Use of a heterobimetallic triangular complex of formula ZnFe₂(μ₃-O)(μ₂-O₂CCF₃)₆(H₂O)₃ as a single-source precursor, solvothermal reaction conditions, absence of hydroxyl groups from the reaction solvent, and the presence of oleylamine are required to achieve well-defined, crystalline, and monodisperse ZnFe₂O₄ nanoparticles. The size of the ZnFe₂O₄ nanocrystals increases as the ratio of oleic acid and oleylamine ligands to precursor increases. The inversion parameter increases with increasing solubility of the precursor in the reaction solvent, with the presence of oleic acid in the reaction mixture, and with decreasing reaction temperature. These results are consistent with a mechanism in which ligand exchange between oleic acid and carboxylate ligands bound to the precursor complex influences the degree to which the reaction produces a kinetically trapped or thermodynamically stable cation distribution. Importantly, these results indicate that preservation of the triangular Zn-O-Fe₂ core structure of the precursor in the reactive monomer species is crucial to the production of a phase-pure ZnFe₂O₄ product and to the ability to tune the cation distribution. Overall, these results demonstrate the advantages of using a single-source precursor and solvothermal reaction conditions to achieve synthetic control over the structure of ternary spinel ferrite nanocrystals.