Structure-Related Electronic and Magnetic Properties in Ultrathin Epitaxial NixFe3-xO4 Films on MgO(001).

Off-stoichiometric NixFe3-xO4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe3O4 to NiFe2O4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe2+ cations are substituted by Ni2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

Real-Time Monitoring of Strain Accumulation and Relief during Epitaxy of Ultrathin Co Ferrite Films with Varied Co Content.

Ultrathin CoxFe3-xO4 films of high structural quality and with different Co content (x = 0.6-1.2) were prepared by reactive molecular beam epitaxy on MgO(001) substrates. Epitaxy of these ferrite films is extensively monitored by means of time-resolved (operando) X-ray diffraction recorded in out-of-plane geometry to characterize the temporal evolution of the film structure. The Co ferrite films show high crystalline ordering and smooth film interfaces independent of their Co content. All CoxFe3-xO4 films exhibit enhanced compressive out-of-plane strain during the early stages of growth, which partly releases with increasing film thickness. When the Co content of the ferrite films increases, the vertical-layer distances increase, accompanied by slightly increasing film roughnesses. The latter result is supported by surface-sensitive low-energy electron diffraction as well as X-ray reflectivity measurements on the final films. In contrast, the substrate-film interface roughness decreases with increasing Co content, which is confirmed with X-ray reflectivity measurements. In addition, the composition and electronic structure of the ferrite films is characterized by means of hard X-ray photoelectron spectroscopy performed after film growth. The experiments reveal the expected increasing Fe3+/Fe2+ cation ratios for a higher Co content.

Cationic Ordering and Its Influence on the Magnetic Properties of Co-Rich Cobalt Ferrite Thin Films Prepared by Reactive Solid Phase Epitaxy on Nb-Doped SrTiO3(001).

Here, we present the (element-specific) magnetic properties and cation ordering for ultrathin Co-rich cobalt ferrite films. Two Co-rich CoxFe3-xO4 films with different stoichiometry (x=1.1 and x=1.4) have been formed by reactive solid phase epitaxy due to post-deposition annealing from epitaxial CoO/Fe3O4 bilayers deposited before on Nb-doped SrTiO3(001). The electronic structure, stoichiometry and homogeneity of the cation distribution of the resulting cobalt ferrite films were verified by angle-resolved hard X-ray photoelectron spectroscopy. From X-ray magnetic circular dichroism measurements, the occupancies of the different sublattices were determined using charge-transfer multiplet calculations. For both ferrite films, a partially inverse spinel structure is found with increased amount of Co3+ cations in the low-spin state on octahedral sites for the Co1.4Fe1.6O4 film. These findings concur with the results obtained by superconducting quantum interference device measurements. Further, the latter measurements revealed the presence of an additional soft magnetic phase probably due to cobalt ferrite islands emerging from the surface, as suggested by atomic force microscope measurements.

Impact of Strain and Morphology on Magnetic Properties of Fe3O4/NiO Bilayers Grown on Nb:SrTiO3(001) and MgO(001).

We present a comparative study of the morphology and structural as well as magnetic properties of crystalline Fe3O4/NiO bilayers grown on both MgO(001) and SrTiO3(001) substrates by reactive molecular beam epitaxy. These structures were investigated by means of X-ray photoelectron spectroscopy, low-energy electron diffraction, X-ray reflectivity and diffraction, as well as vibrating sample magnetometry. While the lattice mismatch of NiO grown on MgO(001) was only 0.8%, it was exposed to a lateral lattice mismatch of −6.9% if grown on SrTiO3. In the case of Fe3O4, the misfit strain on MgO(001) and SrTiO3(001) amounted to 0.3% and −7.5%, respectively. To clarify the relaxation process of the bilayer system, the film thicknesses of the magnetite and nickel oxide films were varied between 5 and 20 nm. While NiO films were well ordered on both substrates, Fe3O4 films grown on NiO/SrTiO3 exhibited a higher surface roughness as well as lower structural ordering compared to films grown on NiO/MgO. Further, NiO films grew pseudomorphic in the investigated thickness range on MgO substrates without any indication of relaxation, whereas on SrTiO3 the NiO films showed strong strain relaxation. Fe3O4 films also exhibited strong relaxation, even for films of 5 nm thickness on both NiO/MgO and NiO/SrTiO3. The magnetite layers on both substrates showed a fourfold magnetic in-plane anisotropy with magnetic easy axes pointing in 100 directions. The coercive field was strongly enhanced for magnetite grown on NiO/SrTiO3 due to the higher density of structural defects, compared to magnetite grown on NiO/MgO.

Plasma Enhanced Complete Oxidation of Ultrathin Epitaxial Praseodymia Films on Si(111).

Praseodymia films have been exposed to oxygen plasma at room temperature after deposition on Si(111) via molecular beam epitaxy. Different parameters as film thickness, exposure time and flux during plasma treatment have been varied to study their influence on the oxygen plasma oxidation process. The surface near regions have been investigated by means of X-ray photoelectron spectroscopy showing that the plasma treatment transforms the stoichiometry of the films from Pr2O3 to PrO2. Closer inspection of the bulk properties of the films by means of synchrotron radiation based X-ray reflectometry and diffraction confirms this transformation if the films are thicker than some critical thickness of 6 nm. The layer distance of these films is extremely small verifying the completeness of the plasma oxidation process. Thinner films, however, cannot be transformed completely. For all films, less oxidized very thin interlayers are detected by these experimental techniques.