Ophiolite-related ultramafic rocks (Serpentinites) in the Caribbean region: a review of their occurrence, composition, origin, emplacements and Ni-Laterite soil formation

Ultramafic rocks, mainly serpentinized peridotites of mantle origin, are mostly associated with the ophiolites of Mesozoic age that occur in belts along three of the margins of the Caribbean plate. The most extensive exposures are in Cuba. The ultramafic-mafic association (ophiolites) were formed and emplaced in several different tectonic environments. Mineralogical studies of the ultramafic rocks and the chemistry of the associated mafic rocks indicate that most of the ultramafic-mafic associations in both the northern and southern margins of the plate were formed in arc-related environments. There is little mantle peridotite exposed in the ophiolitic associations of the west coast of Central America, in the south Caribbean in Curacao and in the Andean belts in Colombia. In these occurrences the chemistry and age of the mafic rocks indicates that this association is mainly part of the 89 Ma Caribbean plateau province. The age of the mantle peridotites and associated ophiolites is probably mainly late Jurassic or Early Cretaceous. Emplacement of the ophiolites possibly began in the Early Cretaceous in Hispaniola and Puerto Rico, but most emplacement took place in the Late Cretaceous to Eocene (e.g. Cuba). Along the northern South America plate margin, in the Caribbean mountain belt, emplacement was by major thrusting and probably was not completed until the Oligocene or even the early Miocene. Caribbean mantle peridotites, before serpentinization, were mainly harzburgites, but dunites and lherzolites are also present. In detail, the mineralogical and chemical composition varies even within one ultramafic body, reflecting melting processes and peridotite/melt interaction in the upper mantle. At least for the northern Caribbean, uplift (postemplacement tectonics) exposed the ultramafic massifs as a land surface to effective laterization in the beginning of the Miocene. Tectonic factors, determining the uplift, exposing the peridotites to weathering varied. In the northern Caribbean, in Guatemala, Jamaica, and Hispaniola, uplift occurred as a result of transpresional movement along pre-existing major faults. In Cuba, uplift occurred on a regional scale, determined by isostatic adjustment. In the south Caribbean, uplift of the Cordillera de la Costa and Serrania del Interior exposing the peridotites, also appears to be related to strike-slip movement along the El Pilar fault system. In the Caribbean, Ni-laterite deposits are currently being mined in the central Dominican Republic, eastern Cuba, northern Venezuela and northwest Colombia. Although apparently formed over ultramafic rocks of similar composition and under similar climatic conditions, the composition of the lateritic soils varies. Factors that probably determined these differences in laterite composition are geomorphology, topography, drainage and tectonics. According to the mineralogy of principal ore-bearing phases, Dominican Ni-laterite deposits are classified as the hydrous silicate-type. The main Ni-bearing minerals are hydrated Mg-Ni silicates (serpentine and ¿garnierite¿) occurring deeper in the profile (saprolite horizon). In contrast, in the deposits of eastern Cuba, the Ni and Cooccurs mainly in the limonite zone composed of Fe hydroxides and oxides as the dominant mineralogy in the upper part of the profile, and are classified as the oxide-type.

X-ray photoelectron spectroscopy analysis of ion¿beam¿induced oxidation of GaAs and AlGaAs

The oxidation of GaAs and AlGaAs targets subjected to O2+ bombardment has been analyzed, using in situ x¿ray photoelectron spectroscopy, as a function of time until steady state is reached. The oxides formed by the O2+ bombardment have been characterized in terms of composition and binding energy. A strong energy and angular dependence for the oxidation of As relative to Ga is found. Low energies as well as near normal angles of incidence favor the oxidation of As. The difference between Ga and As can be explained in terms of the formation enthalpy for the oxide and the excess supply of oxygen. In an AlGaAs target the Al is very quickly completely oxidized irrespective of the experimental conditions. The steady state composition of the altered layers show in all cases a preferential removal of As.

Modifications in the Si valence band after ion-beam-induced oxidation

The changes undergone by the Si surface after oxygen bombardment have special interest for acquiring a good understanding of the Si+-ion emission during secondary ion mass spectrometry (SIMS) analysis. For this reason a detailed investigation on the stoichiometry of the builtup surface oxides has been carried out using in situ x-ray photoemission spectroscopy (XPS). The XPS analysis of the Si 2p core level indicates a strong presence of suboxide chemical states when bombarding at angles of incidence larger than 30°. In this work a special emphasis on the analysis and interpretation of the valence band region was made. Since the surface stoichiometry or degree of oxidation varies with the angle of incidence, the respective valence band structures also differ. A comparison with experimentally measured and theoretically derived Si valence band and SiO2 valence band suggests that the new valence bands are formed by a combination of these two. This arises from the fact that Si¿Si bonds are present on the Si¿suboxide molecules, and therefore the corresponding 3p-3p Si-like subband, which extends towards the Si Fermi level, forms the top of the respective new valence bands. Small variations in intensity and energy position for this subband have drastic implications on the intensity of the Si+-ion emission during sputtering in SIMS measurements. A model combining chemically enhanced emission and resonant tunneling effects is suggested for the variations observed in ion emission during O+2 bombardment for Si targets.

Strain-induced stabilization of new magnetic spinel structures in epitaxial oxide heterostructures.

We report here on the growth of NiFe2O4 epitaxial thin films of different thickness (3 nm ¿ t ¿ 32 nm) on single crystalline substrates having spinel (MgAl2O4) or perovskite (SrTiO3) structure. Ultrathin films, grown on any of those substrates, display a huge enhancement of the saturation magnetization: we will show that partial cationic inversion may account for this enhancement, although we will argue that suppression of antiparallel collinear spin alignment due to size-effects cannot be excluded. Besides, for thicker films, the magnetization of films on MAO is found to be similar to that of bulk ferrite; in contrast, the magnetization of films on STO is substantially lower than bulk. We discuss on the possible mechanisms leading to this remarkable difference of magnetization.

Epitaxial growth of biferroic YMnO3(0001) on platinum electrodes

Epitaxial films of the biferroic YMnO3 (YMO) oxide have been grown on platinum-coated SrTiO3(1 1 1) and Al2O3(0 0 0 1) substrates. The platinum electrodes, (1 1 1) oriented, are templates for the epitaxy of the hexagonal phase of YMO with a (0 0 0 1) out-of-plane orientation, which is of interest as this is the polarization direction of YMO. X-ray diffractometry indicates the presence of two crystal domains, 60° rotated in-plane, in the Pt(1 1 1) layers which subsequently are transferred on the upperlaying YMO. Cross-section analysis by high-resolution transmission electron microscopy (HRTEM) of YMnO3/Pt/SrTiO3(1 1 1) shows high-quality epitaxy and sharp interfaces across the structure in the observed region. We present a detailed study of the epitaxial growth of the hexagonal YMO on the electrodes.

Gas sensing properties of catalytically modified WO3 with copper and vanadium for NH3 detection

Ammonia gas detection by pure and catalytically modified WO3 based gas sensor was analysed. The sensor response of pure WO3 to NH3 was not only rather low but also presented an abnormal behaviour, probably due to the unselective oxidation of ammonia to NOx. Copper and vanadium were introduced in different concentrations and the resulting material was annealed at different temperatures in order to improve the sensing properties for NH3 detection. The introduction of copper and vanadium as catalytic additives improved the response to NH3 and also eliminated the abnormal behaviour. Possible mechanisms of NH3 reaction over these materials are discussed. Sensor responses to other gases like NO2 or CO and the interference of humidity on ammonia detection were also analysed so as to choose the best sensing element.

Enhanced electron-electron correlations in nanometric epitaxial SrRuO3 epitaxial films

Epitaxial and fully strained SrRuO3 thin films have been grown on SrTiO3(100). At initial stages the growth mode is three-dimensional- (3D-)like, leading to a finger-shaped structure aligned with the substrate steps and that eventually evolves into a 2D step-flow growth. We study the impact that the defect structure associated with this unique growth mode transition has on the electronic properties of the films. Detailed analysis of the transport properties of nanometric films reveals that microstructural disorder promotes a shortening of the carrier mean free path. Remarkably enough, at low temperatures, this results in a reinforcement of quantum corrections to the conductivity as predicted by recent models of disordered, strongly correlated electronic systems. This finding may provide a simple explanation for the commonly observed¿in conducting oxides-resistivity minima at low temperature. Simultaneously, the ferromagnetic transition occurring at about 140 K, becomes broader as film thickness decreases down to nanometric range. The relevance of these results for the understanding of the electronic properties of disordered electronic systems and for the technological applications of SrRuO3¿and other ferromagnetic and metallic oxides¿is stressed.

Spin filtering through ferromagnetic BiMnO3 tunnel barriers

We report on experiments of spin filtering through ultrathin single-crystal layers of the insulating and ferromagnetic oxide BiMnO3 (BMO). The spin polarization of the electrons tunneling from a gold electrode through BMO is analyzed with a counterelectrode of the half-metallic oxide La2/3Sr1/3MnO3 (LSMO). At 3 K we find a 50% change of the tunnel resistances according to whether the magnetizations of BMO and LSMO are parallel or opposite. This effect corresponds to a spin-filtering efficiency of up to 22%. Our results thus show the potential of complex ferromagnetic insulating oxides for spin filtering and injection.

Influence of RF power on the properties of sputtered ZnO:Al thin films

Transparent conducting, aluminium doped zinc oxide thin films (ZnO:Al) were deposited by radio frequency (RF) magnetron sputtering. The RF power was varied from 60 to 350Wwhereas the substrate temperature was kept at 160 °C. The structural, electrical and optical properties of the as-deposited films were found to be influenced by the deposition power. The X-ray diffraction analysis showed that all the films have a strong preferred orientation along the [001] direction. The crystallite size was varied from 14 to 36 nm, however no significant change was observed in the case of lattice constant. The optical band gap varied in the range 3.44-3.58 eV. The lowest resistivity of 1.2×10 -3Vcm was shown by the films deposited at 250 W. The mobility of the films was found to increase with the deposition power.

Transparent conducting thin films by the co-sputtering of ZnO-ITO targets

Transparent and conductive Zn-In-Sn-O (ZITO) amorphous thin films have been deposited at room temperature by the rf magnetron co-sputtering of ITO and ZnO targets. Co-sputtering gives the possibility to deposit multicomponent oxide thin films with different compositions by varying the power to one of the targets. In order to make ZITO films with different Zn content, a constant rf power of 50 W was used for the ITO target, where as the rf power to ZnO target was varied from 25 W to 150 W. The as deposited films showed an increase in Zn content ratio from 17 to 67 % as the power to ZnO target was increased from 25 to 150 W. The structural, electrical and optical properties of the as deposited films are reported. The films showed an average transmittance over 80% in the visible wavelength range. The electrical resistivity and optical band gap of the ZITO films were found to depend on the Zn content in the film. The ZITO films deposited at room temperature with lower Zn content ratios showed better optical transmission and electrical properties compared to ITO film.

Electrical and optical properties of Zn-In-Sn-O transparent conducting thin films

Indium tin oxide (ITO) is one of the widely used transparent conductive oxides (TCO) for application as transparent electrode in thin film silicon solar cells or thin film transistors owing to its low resistivity and high transparency. Nevertheless, indium is a scarce and expensive element and ITO films require high deposition temperature to achieve good electrical and optical properties. On the other hand, although not competing as ITO, doped Zinc Oxide (ZnO) is a promising and cheaper alternative. Therefore, our strategy has been to deposit ITO and ZnO multicomponent thin films at room temperature by radiofrequency (RF) magnetron co-sputtering in order to achieve TCOs with reduced indium content. Thin films of the quaternary system Zn-In-Sn-O (ZITO) with improved electrical and optical properties have been achieved. The samples were deposited by applying different RF powers to ZnO target while keeping a constant RF power to ITO target. This led to ZITO films with zinc content ratio varying between 0 and 67%. The optical, electrical and morphological properties have been thoroughly studied. The film composition was analysed by X-ray Photoelectron Spectroscopy. The films with 17% zinc content ratio showed the lowest resistivity (6.6 × 10 - 4 Ω cm) and the highest transmittance (above 80% in the visible range). Though X-ray Diffraction studies showed amorphous nature for the films, using High Resolution Transmission Electron Microscopy we found that the microstructure of the films consisted of nanometric crystals embedded in a compact amorphous matrix. The effect of post deposition annealing on the films in both reducing and oxidizing atmospheres were studied. The changes were found to strongly depend on the zinc content ratio in the films.

Giant step bunching from self-organized coalescence of SrRuO3 islands

Step bunching develops in the epitaxy of SrRuO3 on vicinal SrTiO3(001) substrates. We have investigated the formation mechanisms and we show here that step bunching forms by lateral coalescence of wedgelike three-dimensional islands that are nucleated at substrate steps. After coalescence, wedgelike islands become wider and straighter with growth, forming a self-organized network of parallel step bunches with altitudes exceeding 30 unit cells, separated by atomically flat terraces. The formation mechanism of step bunching in SrRuO3, from nucleated islands, radically differs from one-dimensional models used to describe bunching in semiconducting materials. These results illustrate that growth phenomena of complex oxides can be dramatically different to those in semiconducting or metallic systems.

Dielectric anomaly and magnetic response of epitaxial orthorhombic YMnO3 thin films

The structure, magnetic response, and dielectric response of the grown epitaxial thin films of the orthorhombic phase of YMnO3 oxide on Nb:SrTiO3 (001) substrates have been measured. We have found that a substrate-induced strain produces an in-plane compression of the YMnO3 unit cell. The magnetization versus temperature curves display a significant zero-field cooling (ZFC)-field cooling hysteresis below the Nel temperature (TN 45 K). The dielectric constant increases gradually (up to 26%) below the TN and mimics the ZFC magnetization curve. We argue that these effects could be a manifestation of magnetoelectric coupling in YMnO3 thin films and that the magnetic structure of YMnO3 can be controlled by substrate selection and/or growth conditions.

Kerr measurements on single-domain SrRuO3 thin films

We report on the magneto-optical measurements of an epitaxial SrRuO3 film grown on SrTiO3 (0 0 1), which previously was determined to be single domain orientated by x-ray diffraction and Raman spectroscopy techniques. Our experiments reveal a large Kerr rotation, which reaches a maximum value of about 0.5° at low temperature. By measuring magnetic hysteresis loops at different temperatures, we determined the temperature dependence of the Kerr rotation in the polar configuration. Values of the anisotropic magnetoresistance ~ 20% have been measured. These values are remarkably higher than those of other metallic oxides such as manganites. This striking difference can be attributed to the strong spin-orbit interaction of the Ru 4d ion in the SrRuO3 compound.

Synthesis of sodium-zinc spinel ferrites

The synthesis of spinel ferrites with composition Zn1-2xNaxFe2+xO4has been performed and the composition range in which single phase samples are obtained has been defined. The characterization of the samples has been carried out from atomic absorption and X-ray fluorescence analyses, X-ray diffraction patterns, Mössbauer spectroscopy and thermomagnetic measurements. It is show that significant loss of Na does exist when the synthesis is performed at high temperatures. When the Na volatilization is avoided spinel oxides with Na content up to 0.25 atoms per unit formula can be obtained. In this case the increase of the interatomic distances leads to differing fundamental magnetic properties as compared to the equivalent lithium-zinc ferrites.