Oxygen diffusion and vacancy migration thermally-activated govern high-temperature magnetism in ceria.

Several experimental works currently demonstrate that metallic nano-oxides and carbon nanomaterials expected to be diamagnets, in fact, behave as ferromagnets at room temperature. More than scientifically intriguing, this unconventional and unexpected ferromagnetism pave the way for innovation products and novel nanotechnological applications, gathering the magnetism to interesting functionalities of these nanomaterials. Here, we investigate the non-conventional ferromagnetism observed at high temperatures in nanocrystalline cerium dioxide (CeO2or nanoceria) thin films that are optically transparent to visible light. Nanoceria exhibits several concrete applications in catalytic processes, photovoltaic cells, solid-state fuel cells, among others, which are mostly due to natural presence of oxygen vacancies and easy migration of the oxygen through the structure. The ferromagnetism in non-stoichiometric nanocrystaline ceria can be consistently described by ab initio electronic structure calculations, which support that oxygen vacancies cause the formation of magnetic moments and can provide a robust interconnectivity within magnetic polarons theoretical framework. Additionally, we present a conceptual model to account the oxygen transport to the non-conventional ferromagnetism at temperatures well above room temperature. The approach is complementary to the thermally-activated effective transfers of charge and spin around oxygen vacancy centers.

Grain structure and magnetic relaxation of self-assembled Co nanowires.

The magnetic relaxation of Co nanowires assemblies embedded in CeO(2)/SrTiO(3)(001) epilayers has been investigated by magnetization decay measurements. Two different samples were studied, with nanowires having distinct crystallographic structures and diameters of 3 and 5 nm. The structure of the nanowires was derived from high-resolution transmission electron microscopy analysis. The 3 nm diameter nanowires are made of hcp Co grains with the c-axis pointing along one of the four <111> directions of the CeO(2) matrix, separated by fcc Co regions. In the 5 nm diameter nanowires, the grains are smaller and the density of stacking faults is much higher. The magnetic viscosity coefficient (S) of these two systems was measured as a function of the applied field and of the temperature. Analysis of the variation of S and of the activation volume for magnetization reversal reveals distinct behaviors for the two systems. In the nanowires assembly with 5 nm diameter, the results can be described by considering an energy barrier distribution related to shape anisotropy and are consistent with a thermally activated reversal of the magnetization. In contrast, the anomalous behavior of the 3 nm diameter wires indicates that additional sources of anisotropy have to be considered in order to describe the distribution of energy barriers and the reversal process. The distinct magnetic behaviors observed in these two systems can be rationalized by considering the grain structure of the nanowires and the resulting effective magnetocrystalline anisotropy.

Mechanism of localization of the magnetization reversal in 3 nm wide Co nanowires.

The mechanism of magnetization reversal has been studied in a model system of self-assembled cobalt nanowires with a 3 nm diameter. The structure, orientation and size of grains within the nanowires could be determined by high resolution transmission electron microscopy. The magnetic properties were probed using static and dynamic magnetization measurements. Micromagnetic modeling based on the structural analysis allows us to correlate the structure and the magnetic behavior of the wires, revealing competition between shape anisotropy, magnetocrystalline anisotropy and exchange in the localized reversal within Co hcp oriented grains. These results provide direct experimental evidence of the link between anisotropy fluctuations and reversal localization in nanowires.

Ferromagnetism induced by oxygen and cerium vacancies above the percolation limit in CeO2.

We studied the structural, chemical and magnetic properties of non-doped ceria (CeO(2)) thin films electrodeposited on silicon substrates. Experimental results confirm that the observed room temperature ferromagnetism is driven by both cerium and oxygen vacancies. We investigated ceria films presenting vacancy concentrations well above the percolation limit. Irradiation experiments with neon ions were employed to generate highly oxygen defective CeO(2-δ) structures. X-ray photoelectron spectroscopy and x-ray absorption near-edge structure spectroscopy were used to estimate the concentration of Ce(3+) sites in the films, which can reach up to 50% of Ce(3+) replacing Ce(4+), compared to a stoichiometric CeO(2) structure. Despite the increment of structural disorder, we observe that the saturation magnetization continuously increases with Ce(3+) concentration. Our experiments demonstrate that the ferromagnetism observed in ceria thin films, highly disordered and oxygen-deficient, preserving the fluorite-type structure only in a nanometer scale, remains intrinsically stable at room temperature.

Electrochemical preparation of overlapped porous layers on anodic alumina.

In this paper, we report the development of a new architecture on porous anodic alumina using the conventional two-step anodization method. The samples prepared in two identical steps using galvanostatic anodization exhibited two porous layers overlapped with distinct pore area distributions. The effects from the first anodization time and temperature on this different morphology were assessed using Factorial Design. The chemical removal time of the oxide formed during the first anodization was not relevant for the overlapped porous structure. The most important factor was the time of the first anodization required for formation of stable patterns on the substrate, which would be reproduced in the second anodization. A pore mismatch appeared because under galvanostatic control the changes in the actual area become important, which is not the case for sample preparation under potentiostatic control where the current density is adjusted according to the new boundary condition. The new architecture with mismatching layers may open the way for further applications of porous alumina as template for nanomaterial.

Magnetic properties of synthetic eumelanin--preliminary results.

We report an experimental and theoretical study of magnetic properties of synthetic eumelanin. The magnetization curves are determined by using both a vibrating sample magnetometer and a superconducting quantum interferometer device in an extended range of magnetic fields ranging from -10 kOe to 10 kOe at different temperatures. We find that the eumelanin magnetization can be qualitatively explained in terms of a simple model of dipolar spheres with an intrinsic magnetic moment. The latter one is experimentally measured by using X-band electron paramagnetic resonance. Our findings indicate that synthetic melanins are superparamagnetic.