Raman studies of cation distribution and thermal stability of epitaxial spinel NiCo2O4 films

Epitaxial thin films of spinel NiCo2O4 (NCO) grown on MgAl2O4 (001) substrates are reported to exhibit dramatic changes in the magnetic and transport properties with deposition temperature. While films grown at lower temperatures (< 450 degrees C) are ferrimagnetic with metallic characteristics, those grown at higher temperatures are non-magnetic and insulating. Detailed polarized Raman spectroscopy studies indicate that the higher temperature films have close to the ideal inverse spinel cation distribution, Co3+[Ni2+Co3+]O-4(2-), whereas those deposited at lower temperature are characterized by mixed cation/charge distribution at both the tetragonal (A) and octahedral (B) sites. Additionally, temperature-dependent Raman studies demonstrate that, unlike bulk polycrystalline samples, all the NCO films are robust against thermal treatment with full reversibility after annealing at 600 degrees C in oxygen and air. However, partial decomposition is observed after annealing in vacuum. (C) 2013 AIP Publishing LLC.