Reducible oxides as ultrathin epitaxial films

This chapter reviews and discusses recent work on two-dimensional films of reducible oxides supported on metal substrates. In general, peculiar chemical and structural phases, different from the bulk ones, can be stabilized depending on the oxygen chemical potential, on kinetic processes and on the specific substrate used. A peculiarity of reducible oxides is that the observed phases can often be reversibly transformed one into the other by applying reducing and oxidizing treatments

Morphology and Optical Properties of Gas-Phase-Synthesized Plasmonic Nanoparticles: Cu and Cu/MgO

In this paper, an investigation of the properties of Cu and Cu/MgO nanoparticles (NPs) is presented. The NPs were obtained with gas-phase synthesis, and the MgO shells or matrices were formed via the co-deposition method on inert substrates. SEM and AFM were used to investigate the NP morphology on Si/SiOx, quartz, and HOPG. The Cu NPs revealed flattening of their shape, and when they were deposited on HOPG, diffusion and formation of small chains were observed. The embedding of Cu NPs in MgO was confirmed by TEM and EDX maps. XPS showed that Cu was in its metallic state, regardless of the presence of the surrounding MgO. UV–Vis revealed the presence of an intense localized surface plasmon resonance (LSPR) for Cu/MgO and for “bare” NPs. These results confirmed the role of MgO as a protective transparent medium for Cu, and the wavelength position of the LSPR in the Cu/MgO system was consistent with calculations. The wavelength position of the LSPR observed for “bare” and post-oxidized Cu NPs was probably affected by the formation of copper oxide shells after exposure to air. This study paves the way for the use of Cu/MgO NPs as plasmonic nanomaterials in applications such as photovoltaics and sensor technology

Influence of defect distribution on the reducibility of CeO2-x nanoparticles

Ceria nanoparticles (NPs) are fundamental in heterogeneous catalysis because of their ability to store or release oxygen depending on the ambient conditions. Their oxygen storage capacity is strictly related to the exposed planes, crystallinity, density and distribution of defects. In this work a study of ceria NPs produced with a ligand-free, physical synthesis method is presented. The NP films were grown by a magnetron sputtering based gas aggregation source and studied by high resolution- and scanning-transmission electron microscopy and x-ray photoelectron spectroscopy. In particular, the influence of the oxidation procedure on the NP reducibility has been investigated. The different reducibility has been correlated to the exposed planes, crystallinity and density and distribution of structural defects. The results obtained in this work represent a basis to obtain cerium oxide NP with desired oxygen transport properties

The effect of composition on structural, thermal, redox and bioactive properties of Ce-containing glasses

The effect of phosphate on the ability of Ce-containing bioactive glasses to inhibit oxidative stress was studied on compositions based on Hench (46.2%SiO224.3%Na2O26.9ÊO2.6P2O5, mol%) and Kokubo (50.0%SiO225.0%Na2O25.0ÊO) glasses. In particular, the reduction of catalase mimetic activity of Ce-containing glasses due to the presence: i) of P2O5 in the glass compositions, and ii) of phosphate groups in the solution employed for catalase mimetic activity tests was explained and rationalized by combining SEM, XPS, XRD, DTA, FT-IR and UV-vis experiments with Molecular Dynamics simulations.The results suggest that the Ce ions play a different structural role in the two series of glasses. In particular, in phosphate free glasses Ce is coordinated by non-bridging oxygens (NBOs) originated from the disruption of the silicate network, whereas in phosphate containing glasses the NBOs around Ce ions belong to orthophosphate groups. The latter groups stabilize the Ce3+ species subtracting them from the interconversion process between Ce3+ and Ce4+, which is of fundamental importance for the exhibition of the catalase mimetic activity

Steering the magnetic properties of Ni/NiO/CoO core-shell nanoparticle films: The role of core-shell interface versus interparticle interactions

Supported core-shell Ni/NiO/CoO nanoparticle (NP) films were obtained by deposition of preformed and mass-selected Ni NPs on a buffer layer of CoO, followed by a top CoO layer. The resulting NPs have core/shell morphology, with a McKay icosahedral Ni core and a partially crystalline CoO shell. X-ray photoelectron spectroscopy evidenced the presence of a thin NiO layer, which was shown to be between the Ni core and the CoO shell by elemental TEM mapping. CoO and NiO shells with different thickness values were obtained, allowing us to investigate the evolution of the magnetic properties of the NP assemblies as a function of the oxide shell thickness. Both exchange-coupling and magnetostatic interactions significantly contribute to the magnetic behavior of Ni/NiO/CoO NP films. After the Ni/NiO/CoO NPs are cooled in a weak magnetic field, they have blocking temperature higher than room temperature because of strong magnetostatic interactions, which support the formation of a spin-glass-like state below similar to 250 K. Exchange coupling dominates the magnetic behavior after the NPs are cooled in a strong magnetic field. The exchange bias (EB) is in the 0.17-2.35 kOe range and strongly depends on the CoO thickness (0.4-2.7 nm), showing the onset of the EB at the few-nanometer scale. The switching field distribution showed that the EB opposes the magnetization reversal from the direction along the cooling field but it does not significantly ease the opposite process. The EB depends on t(CoO) only for t(NiO) <= 0.5 nm, but when NiO is 0.7 nm thick it strongly interacts with CoO and a large increase of the EB and coercivity is observed

Role of cerium oxide in bioactive glasses during catalytic dissociation of hydrogen peroxide

The addition of cerium oxide to bioactive glasses, important materials for bone tissue regeneration, has been shown to induce multifunctionality, combining a significant bioactivity with antioxidant properties. We provide a real time investigation of the evolution of the electronic properties of highly diluted cerium ions in a liquid environment containing hydrogen peroxide - the most abundant reactive oxygen species in living cells. This challenging task is undertaken by means of high-energy resolution fluorescence detected by X-ray absorption near-edge spectroscopy at the Ce L-3 edge. We investigate samples with variable compositions and different morphologies. We relate the observed spectroscopic changes not only to variations in the concentration of the two Ce oxidation states in the samples, but also to changes in the local atomic environment of Ce ions, providing a clear picture of the role of cerium ions in the dissociation of hydrogen peroxide. The obtained results contribute to the understanding of the mechanisms that come into play in the process and provide a basis for the optimization of the functionalities of this class of materials

Contraction, cation oxidation state and size effects in cerium oxide nanoparticles

An accurate description of the structural and chemical modifications of cerium oxide nanoparticles (NPs) is mandatory for understanding their functionality in applications. In this work we investigate the relation between local atomic structure, oxidation state, defectivity and size in cerium oxide NPs with variable diameter below 10 nm, using x-ray absorption fine structure analysis in the near and extended energy range. The NPs are prepared by physical methods under controlled conditions and analyzed in morphology and crystalline quality by high resolution transmission electron microscopy. We resolve here an important question on the local structure of cerium oxide NPs: we demonstrate a progressive contraction in the Ce-O interatomic distance with decreasing NP diameter and we relate the observed effect to the reduced dimensionality. The contraction is not significantly modified by inducing a 4%-6% higher Ce3+ concentration through thermal annealing in high vacuum. The consequences of the observed average cation-anion distance contraction on the properties of the NPs are discussed

Role of interface and morphology in the magnetic behaviour of perpendicular thin films based on L10 FePt

FePt L10 ordered alloy is a promising material for high-density magnetic recording, since it allows the ferromagnetic stability in particles of few nanometers. Here we present our recent studies on the correlation between magnetic and morphological/interfacial properties of FePt -based thin films, nanostructures, and nano-composite bilayers. L10 FePt (001) epitaxial thin films with high structural quality were grown on (100) MgO by sputtering r.f., using the alternate-layer deposition method. By playing with growth temperature on the one hand and post-annealing temperature and time on the other, we have been able to finely control epitaxy, structural order, and morphology from 3D laterally confined structures to continuous film, with desired grain size. In particular we have been able to decrease grain size and to optimise magnetic properties (increase of anisotropy/coercivity ratio) at the same time, by post-annealing in situ [1]. Laterally confined magnetic structures were also obtained by focused ion beam (FIB). We have shown that for suitable Ga+ doses (1?1014 ion/cm2), it is possible to transform the L10 ordered phase to the A1 disordered one, without affecting morphology, giving rise to substantial modifications of magnetic properties from hard to soft. Perpendicular 2D magnetic patterns (dots, stripes) in a soft easy-plane matrix were realized in films of continuous morphology [2]. FePt L10 has also been exploited as the hard layer of nanostructured hard-soft nanocomposite bilayers. The exploitation of the exchange-coupling between hard and soft layers in exchange-coupled media represents a possible approach to overcome the so-called "recording trilemma" [3]. The samples were prepared by growing a magnetically soft Fe layer (2 and 3.5 nm) over a hard FePt(001) layer (10 nm). Three bilayers series have been grown based on FePt epitaxial layers with high degree of chemical order (S&#8805;0.76) and different morphologies, corresponding to different interface characteristics. The resulting hard layer anisotropy is high (K>1?107 erg/cm3), and the coercivity is increased by the grains separation (from 1.7 to 3 T). In the Fe/FePt bilayers the coercivity HC is strongly reduced compared to the hard layer value (HC/HChard down to 0.37), indicating that high anisotropy perpendicular systems with moderate coercivity can be obtained [4]. Moreover, the control of the interface morphology allows to modify the magnetic regime at fixed Fe thickness (Rigid Magnet to Exchange-Spring), due to the nanoscale structure effect on the hard/soft coupling, and to tailor the hysteresis loop characteristics

Nanoparticle Langmuir-Blodgett Arrays for Sensing of CO and NO2 Gases

Metal oxide sensors with active Fe2O3 and CoFe2O4 nanoparticle arrays were studied. Sensing nanoparticle films from 1, 2, 4 or 7 monolayers were deposited by Langmuir-Blodgett technique. Sensors are formed on the alumina substrates equipped with heating meander. Langmuir-Blodgett layers were heated or UV irradiated to remove the insulating surfactant. Sensing properties were studied towards CO or NO2 gases in concentrations between 0.5 and 100 ppm in mixture with the dry air. Best response values Igas/Iair were obtained with CoFe2O4 device being 3 for 100 ppm of CO and with Fe2O3 device being (38)-1 for 0.5 ppm of NO2