Growth and characterization of CoO ultra thin films

In this report we present the growth process of the cobalt oxide system using reactive electron beam deposition. In that technique, a target of metallic cobalt is evaporated and its atoms are in-flight oxidized in an oxygen rich reactive atmosphere before reaching the surface of the substrate. With a trial and error procedure the deposition parameters have been optimized to obtain the correct stoichiometry and crystalline phase. The evaporation conditions to achieve the correct cobalt oxide salt rock structure, when evaporating over amorphous silicon nitride, are: 525 K of substrate temperature, 2.5·10-4 mbar of oxygen partial pressure and 1 Å/s of evaporation rate. Once the parameters were optimized a set of ultra thin film ranging from samples of 1 nm of nominal thickness to 20nm thick and bulk samples were grown. With the aim to characterize the samples and study their microstructure and morphology, X-ray diffraction, transmission electron microscopy, electron diffraction, energy dispersive X-ray spectroscopy and quasi-adiabatic nanocalorimetry techniques are utilised. The final results show a size dependent effect of the antiferromagnetic transition. Its Néel temperature becomes depressed as the size of the grains forming the layer decreases.

Efecto de la microestructura en el comportamiento mecánico de aceros de herramienta para trabajo en frío

El estudio desarrollado en la tesis doctoral profundiza en las relaciones existentes entre la microestructura y el comportamiento a rotura y fatiga de tres tipos de Aceros de Herramienta para trabajo en Frío, dos obtenidos por colada y un tercero mediante pulvimetalúrgia. En primer lugar se evaluaron los aspectos microestructurales relacionados con las dos vias de procesamiento empleadas, además del efecto del cambio en la composición química. Asimismo se documentó la influencia del trabajado en caliente sobre la isotropía microestructural. Considerando las caracteristicas microestructurales se evaluó el comportamiento a rotura en tres orientaciones referidas al sentido de la deformación en caliente. Para ello , se empleó la Mecánica de la Fractura Elástica Lineal como marco analítico. Los resultados fueron tratados siguiendo la estadística de Weibull. Para el caso de los aceros colados se implementa un analisis de curva-R para explicar el crecimiento subcrítico de grietas observado experimentalmente. El estudio del comportamiento a fatiga incluyó la determinación del limite a fatiga para todas la orientaciones microestructurales escogidas y el estudio de la cinetica de propagación de fisuras físicamente pequeñas para la orientación con mejor respuesta mecánica.

Preparation and properties of starch-based biopolymers modified with difunctional isocyanates

The present work reports on the preparation of thermoplastic starch (TPS) modified in situ with a diisocyanate derivative. Evidence of the condensation reaction between the hydroxyl groups of starch and glycerol with the isocyanate function (NCO) was confirmed by FTIR analysis. The evolution of the properties of the ensuing TPS, in term of mechanical properties, microstructure, and water sensitivity, was investigated using tensile mechanical, dynamic mechanical thermal analysis (DMTA), X-ray diffraction (XRD), and water uptake. The results showed that the addition of isocyanate did not affect the crystallinity of the TPS and slightly reduced the water uptake of the material. The evolution of the mechanical properties with ageing became less pronounced by the addition of the isocyanate as their amount exceeded 4 to 6wt%.

Market Transparency, Market Quality and Sunshine Trading

This paper analyzes the implications of pre-trade transpareny on market performance. We find that transparency increases the precision held by agents, however we show that this increase in precision may not be due to prices themselves. In competitive markets, transparency increases market liquidity and reduces price volatility, whereas these results may not hold under imperfect competition. More importantly, market depth and volatility might be positively related with proper priors. Moreover, we study the incentives for liquidity traders to engage in sunshine trading. We obtain that the choice of sunshine/dark trading for a noise trader is independent of his order size, being the traders with higher liquidity needs more interested in sunshine trading, as long as this practice is desirable. Key words: Market Microstructure, Transparency, Prior Information, Market Quality, Sunshine Trading

Market versus limit orders in an imperfectly competitive security

This paper analyzes the choice between limit and market orders in animperfectly competitive noisy rational expectations economy. There is a uniqueinsider, who takes into account the effect their trading has on prices. If theinsider behaves as a price taker, she will choose market orders if her privateinformation is very precise and she will choose limit orders otherwise. On thecontrary, if the insider recognizes and exploits her ability to affect themarket price, her optimal choice is to place limit orders whatever the precisionof her private information.

Minimum price variations, time priority and quotes dynamics

We analyze the impact of a minimum price variation (tick) and timepriority on the dynamics of quotes and the trading costs when competitionfor the order flow is dynamic. We find that convergence to competitiveoutcomes can take time and that the speed of convergence is influencedby the tick size, the priority rule and the characteristics of the orderarrival process. We show also that a zero minimum price variation is neveroptimal when competition for the order flow is dynamic. We compare thetrading outcomes with and without time priority. Time priority is shownto guarantee that uncompetitive spreads cannot be sustained over time.However it can sometimes result in higher trading costs. Empiricalimplications are proposed. In particular, we relate the size of thetrading costs to the frequency of new offers and the dynamics of theinside spread to the state of the book.

Analysis by optical absorption and transmission electron microscopy of the strain inhomogeneities in InGaAs/InP strained layers

Optical absorption spectra and transmission electron microscopy (TEM) observations on InGaAs/InP layers under compressive strain are reported. From the band¿gap energy dispersion, the magnitude of the strain inhomogeneities. Is quantified and its microscopic origin is analyzed in view of the layer microstructure. TEM observations reveal a dislocation network at the layer interface the density of which correlates with ¿¿. It is concluded that local variations of dislocation density are responsible for the inhomogeneous strain field together with another mechanism that dominates when the dislocation density is very low.

Properties of nitrogen doped silicon films deposited by low-pressure chemical vapor deposition from silane and ammonia

Nitrogen doped silicon (NIDOS) films have been deposited by low-pressure chemical vapor deposition from silane SiH4 and ammonia NH3 at high temperature (750°C) and the influences of the NH3/SiH4 gas ratio on the films deposition rate, refractive index, stoichiometry, microstructure, electrical conductivity, and thermomechanical stress are studied. The chemical species derived from silylene SiH2 into the gaseous phase are shown to be responsible for the deposition of NIDOS and/or (silicon rich) silicon nitride. The competition between these two deposition phenomena leads finally to very high deposition rates (100 nm/min) for low NH3/SiH4 gas ratio (R¿0.1). Moreover, complex variations of NIDOS film properties are evidenced and related to the dual behavior of the nitrogen atom into silicon, either n-type substitutional impurity or insulative intersticial impurity, according to the Si¿N atomic bound. Finally, the use of NIDOS deposition for the realization of microelectromechanical systems is investigated.

A time-domain method for the analysis of thermal impedance response preserving the convolution form

The study of the thermal behavior of complex packages as multichip modules (MCM¿s) is usually carried out by measuring the so-called thermal impedance response, that is: the transient temperature after a power step. From the analysis of this signal, the thermal frequency response can be estimated, and consequently, compact thermal models may be extracted. We present a method to obtain an estimate of the time constant distribution underlying the observed transient. The method is based on an iterative deconvolution that produces an approximation to the time constant spectrum while preserving a convenient convolution form. This method is applied to the obtained thermal response of a microstructure as analyzed by finite element method as well as to the measured thermal response of a transistor array integrated circuit (IC) in a SMD package.

Effects of prior hydrogenation on the structure and properties of thermally nanocrystallized silicon layers

Nanocrystalline silicon layers have been obtained by thermal annealing of films sputtered in various hydrogen partial pressures. The as-deposited and crystallized films were investigated by infrared, Raman, x-ray diffraction, electron microscopy, and optical absorption techniques. The obtained data show evidence of a close correlation between the microstructure and properties of the processed material, and the hydrogen content in the as-grown deposit. The minimum stress deduced from Raman was found to correspond to the widest band gap and to a maximum hydrogen content in the basic unannealed sample. Such a structure relaxation seems to originate from the so-called "chemical annealing" thought to be due to Si-H2 species, as identified by infrared spectroscopy. The variation of the band gap has been interpreted in terms of the changes in the band tails associated with the disorder which would be induced by stress. Finally, the layers originally deposited with the highest hydrogen pressure show a lowest stress-which does not correlate with the hydrogen content and the optical band gap¿and some texturing. These features are likely related to the presence in these layers of a significant crystalline fraction already before annealing.

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.

Anomalous crystallization of hydrogenated amorphous silicon during fast heating ramps

Thermal crystallization experiments carried out using calorimetry on several a-Si:H materials with different microstructures are reported. The samples were crystallized during heating ramps at constant heating rates up to 100 K/min. Under these conditions, crystallization takes place above 700 C and progressively deviates from the standard kinetics. In particular, two crystallization processes were detected in conventional a-Si:H, which reveal an enhancement of the crystallization rate. At100 K/min, such enhancement is consistent with a diminution of the crystallization time by a factor of 7. In contrast, no systematic variation of the resulting grain size was observed. Similar behavior was also detected in polymorphous silicon and silicon nanoparticles, thus showing that it is characteristic of a variety of hydrogenated amorphous silicon materials.

Magnetic microstructures from magnetic force microscopy and Monte Carlo simulation in CoFe-Ag-Cu granular films

CoFe-Ag-Cu granular films, prepared by rf sputtering, displayed magnetic domain microstructures for ferromagnetic concentrations above about 32% at, and below the percolation threshold. All samples have a fcc structure with an (111) texture perpendicular to the film plane. Magnetic force microscopy (MFM) showed a variety of magnetic domain microstructures, extremely sensitive to the magnetic history of the sample, which arise from the balance of the ferromagnetic exchange, the dipolar interactions and perpendicular magnetocrystalline anisotropy, MFM images indicate that in virgin samples, magnetic bubble domains with an out-of-plane component of the magnetization are surrounded by a quasicontinuous background of opposite magnetization domains. The application of a magnetic field in different geometries drastically modifies the microstructure of the system in the remanent state: i) for an in-plane field, the MFM images show that most of the magnetic moments are aligned along the film plane, ii) for an out-of-plane field, the MFM signal increases about one order of magnitude, and out-of-plane striped domains with alternating up and down magnetization are stabilized. Numerical simulations show that a variety of metastable domain structures (similar to those observed experimentally) can be reached, depending on magnetic history, in systems with competing perpendicular anisotropy, exchange and dipolar interactions.

Magnetic properties and giant magnetoresistance in melt-spun CoCu alloys

Magnetic, structural, and transport properties of as quenched and annealed Co10Cu90 samples have been investigated using x¿ray diffraction and a SQUID magnetometer. The largest value of MR change was observed for the as¿quenched sample annealed at 450°C for 30 min. The magnetic and transport properties closely correlate with the microstructure, mainly with Co magnetic particle size and its distribution. For thermal annealing the as quenched samples below 600°C, the Co particle diameters increase from 4.0 to 6.0 nm with a magnetoresistance (MR) drop from 33.0% to 5.0% at 10 K. Comparison with the theory indicates that the interfacial electron spin¿dependent scattering mechanism correlates with GMR for Co particle diameters up to about 6.0 nm.

From demagnetizing to magnetizing interactions in CoFe-AgCu granular films

CoFe-AgCu granular films of compositions ranging from 0.17-0.44 ferromagnetic atomic concentration were prepared by rf sputtering. The microstructure and the transport and magnetic properties suggested that this family of samples can be classified into two groups with a crossover concentration at about 32 at. %. The experimental results for samples Co34Fe8Ag54Cu4 and Co18Fe8Ag70Cu4, which are representative of both different behaviors, are discussed. For the as-prepared sample with higher CoFe content, an uncompensated out-of-plane antiferromagneticlike microstructure with dominant demagnetizing interactions was observed. The particle growth through the annealing led to large in-plane ferromagneticlike clusters with dominant magnetizing interactions. The thermal dependence of the remanence-to-saturation ratio of the as-prepared and annealed samples indicated the existence of a high degree of magnetic correlations leading to a very low magnetoresistivity: In none of the cases was a Stoner¿Wohlfarth behavior observed. On the contrary, for the sample with lower CoFe content, the magnetoresistivity change was much higher, and the remanence followed the expected behavior, since magnetic correlations were strongly reduced through dilution.