ABSTRACT
Exchange bias (EB) effects linked to surface spin freezing (SSF) are commonly found in iron oxide nanoparticles, while signatures of SSF in low-field temperature-dependent magnetization curves have been much less frequently reported. Here, we present magnetic properties of dense assemblies of similar-sized (â¼8 nm diameter) particles synthesized by a magnetite (sample S1) and a maghemite (sample S2) method, and the influence of long-term (4 year) sample aging under ambient conditions on these properties. The size of the EB field of the different sample (fresh or aged) states is found to correlate with (a) whether a low-temperature hump feature signaling the SSF transition is detected in out-of-phase ac susceptibility or zero-field-cooled (ZFC) dc magnetization recorded at low field and with (b) the prominence of irreversibility between FC and ZFC curves recorded at high field. Sample S1 displays a lower magnetization than S2, and it is in S1 where the largest SSF effects are found. These effects are significantly weakened by aging but remain larger than the SSF effects in S2, where the influence of aging is considerably smaller. A non-saturating component due to spin disorder in S1 also weakens with aging, accompanied by, we infer, an increase in the superspin and the radius of the ordered nanoparticle cores. X-ray diffraction and Mössbauer spectroscopy provide indication of maghemite-like stoichiometry in both aged samples as well as thicker disordered particle shells in aged-S1 relative to aged-S2 (crystallographically-disordered and spin-disordered according to diffraction and Mössbauer, respectively). The pronounced diminution in SSF effects with aging in S1 is attributed to a (long-term) transition, caused by ambient oxidation, from magnetite-like to maghemite-like stoichiometry, and a concomitant softening of the spin-disordered shell anisotropy. We assess the impact of this anisotropy on the nature of the blocking of the nanoparticle superspins.
ABSTRACT
This paper aims to analyze the competition of single particle anisotropy and interparticle interactions in nanoparticle ensembles using a random anisotropy model. The model is first applied to ideal systems of non-interacting and strongly dipolar interacting ensembles of maghemite nanoparticles. The investigation is then extended to more complex systems of pure cobalt ferrite CoFe2O4 (CFO) and mixed cobalt-nickel ferrite (Co,Ni)Fe2O4 (CNFO) nanoparticles. Both samples were synthetized by the polyol process and exhibit the same particle size (DTEM ≈ 5 nm), but with different interparticle interaction strengths and single particle anisotropy. The implementation of the random anisotropy model allows investigation of the influence of single particle anisotropy and interparticle interactions, and sheds light on their complex interplay as well as on their individual contribution. This analysis is of fundamental importance in order to understand the physics of these systems and to develop technological applications based on concentrated magnetic nanoparticles, where single and collective behaviors coexist.
ABSTRACT
Porous films of Co/CoO magnetic nanoparticles have been obtained by inert gas condensation and partially oxidized in situ in the deposition chamber. These nanoparticle films were subjected to thermal treatments in high vacuum and the chemical and structural changes monitored by x-ray diffraction, transmission electron microscopy, transport and magnetic measurements (with a focus on the exchange-bias phenomenon), which evidence that for vacuum annealing temperatures above 360 °C, most of the CoO phase is reduced to metallic Co without requiring the presence of an external reducing agent (e.g., H2) or a plasma. Additionally, there is a certain degree of particle coalescence resulting in the formation of greater nanoparticles as the annealing temperature increases. This yields a smaller proportion of CoO compared to metallic Co and a reduction of the Co/CoO interface density, pinpointed by a drastic decrease of the exchange-bias field. The crucial roles of the vacuum level and the surface-to-volume ratio are evidenced by magnetic measurements, highlighting the potential of magnetometry as a probe for the reduction/oxidation of composite nanostructures.
ABSTRACT
We report on the unexpected deterioration under ambient conditions of films of Co clusters capped with relatively thick (>100 nm) Cu (or Ti) layers deposited by either thermal evaporation or by radiofrequency sputtering. The magnetic character of the clusters, prepared by gas-phase condensation, allows monitoring the oxidation of the samples through the decay of the saturation magnetization, which takes place on a timescale of days. By contrast, diluted (<10 at.%) cluster-assembled granular Co:Cu films, prepared by co-deposition of the Co clusters with a Cu vapour, are perfectly stable under ambient conditions. We tentatively explain the oxidation of the cluster films as stemming from their very high porosity.
