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°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+]O42−, 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°C in oxygen and air. However, partial decomposition is observed after annealing in vacuum.

Semiconducting n-type nanostructured hematite (α-Fe 2 O 3 ) is a promising photocatalyst for solar water splitting because of its favorable band gap of 2.2 eV, low cost, and abundance in nature. However, its photoactivity is limited by the poor absorptivity and short hole diffusion length. Surface plasmon resonance (SPR) of metallic (Au, Ag, and Cu) nanostructures is known to concentrate and scatter incident light over a broad wavelength range and holds the promise of enhancing the light absorption cross section of a semiconducting material around the plasmonic structures. Herein we report enhanced photoelectrochemical (PEC) performance of a smooth chemical vapor deposited hematite film embedded with Au nanoparticles (NPs). About 3 times higher light absorption and photocurrent enhancement are obtained from thin hematite films containing Au NPs than with pristine hematite films. The plasmonic enhancement increases with the amount of Au NPs for the same thickness of hematite. Thickness-dependent study of photoactivity indicates a higher enhancement in hematite thin films compared to thicker films due to reduced charge transport distance and optimal local field enhancement effect. The improved embedded configuration also has the advantage of consistent performance and protection of plasmonic nanostructures from electrochemical corrosion, resulting in long cycles of operation.

Nanoscale optical band gap variations in epitaxial thin films of two different spinel ferrites, i.e., NiFe2O4 (NFO) and CoFe2O4 (CFO), have been investigated by spatially resolved high resolution electron energy loss spectroscopy. Experimentally, both NFO and CFO show indirect/direct band gaps around 1.52 eV/2.74 and 2.3 eV, and 1.3 eV/2.31 eV, respectively, for the ideal inverse spinel configuration with considerable standard deviation in the band gap values for CFO due to various levels of deviation from the ideal inverse spinel structure. Direct probing of the regions in both the systems with tetrahedral A site cation vacancy, which is distinct from the ideal inverse spinel configuration, shows significantly smaller band gap values. The experimental results are supported by the density functional theory based modified Becke-Johnson exchange correlation potential calculated band gap values for the different cation configurations.

The effect of B-site cation ordering on the room temperature structural and ferromagnetic resonance (FMR) properties of single crystal spinel lithium ferrite (LiFe5O8, LFO) have been investigated. A detailed microstructural analysis is done through X-ray diffraction, polarized Raman spectroscopy, and transmission electron microscopy (TEM) to examine the effect of post-annealing on the B-site cation ordering. The X-ray diffraction pattern of the as-grown crystal indicates a disordered state of the crystal. However, the annealed sample shows additional superlattice reflections corresponding to the ordered phase. This ordering is further confirmed by Raman spectra and TEM images, which reveal ordering of Li and Fe ions at the octahedral sites contrasting with the relatively high degree of octahedral site disorder in the as-grown crystal. To study the effect of B-site ordering on the magnetic properties and FMR linewidth, vibrating sample magnetometry and broadband FMR measurements have been performed for both the ordered and disordered phases of lithium ferrite. The value of saturation magnetization for both phases is ∼290 emu/cm3. A single mode FMR profile is observed for both phases with little distortion. The linewidth characteristics of the ordered and disordered phases of lithium ferrite phases are compared, and it is observed that the linewidth is independent of the cation ordering. Both the phases exhibit a low linewidth (∼26 Oe at 30 GHz) and the effective damping parameter for the as-grown and annealed samples is determined to be 0.0021 ± 0.0001.

The direct liquid injection chemical vapor deposition (DLI-CVD) technique has been used for the growth of cobalt ferrite (CFO) films on (100)-oriented MgAl 2 O 4 (MAO) substrates. Smooth and highly epitaxial cobalt ferrite thin films, with the epitaxial relationship MAO(100) [001] CFO (100) [001], are obtained under optimized deposition conditions. The films exhibit bulk-like structural and magnetic properties with an out-of-plane lattice constant of 8.370Å and a saturation magnetization of 420 kA/m at room temperature. The Raman spectra of films on MgAl 2 O 4 support the fact that the Fe 3+ -and the Co 2+ -ions are distributed in an ordered fashion on the B-site of the inverse spinel structure. The DLI-CVD technique has been extended for the growth of smooth and highly oriented cobalt ferrite thin films on a variety of other substrates, including MgO, and piezoelectric lead magnesium niobate-lead titanate and lead zinc niobate-lead titanate substrates.